CN105209003A - Consumer products comprising silane-modified oils - Google Patents

Consumer products comprising silane-modified oils Download PDF

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Publication number
CN105209003A
CN105209003A CN201480025522.5A CN201480025522A CN105209003A CN 105209003 A CN105209003 A CN 105209003A CN 201480025522 A CN201480025522 A CN 201480025522A CN 105209003 A CN105209003 A CN 105209003A
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CN
China
Prior art keywords
oil
silane
modified
product
consumer products
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Pending
Application number
CN201480025522.5A
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Chinese (zh)
Inventor
J·A·沃斯
L·A·匝诺尼
R·K·帕纳戴克
B·A·舒伯特
N·R·惠特莉
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Procter and Gamble Ltd
Procter and Gamble Co
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Procter and Gamble Ltd
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Publication of CN105209003A publication Critical patent/CN105209003A/en
Pending legal-status Critical Current

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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/92Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof
    • A61K8/922Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof of vegetable origin
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/89Polysiloxanes
    • A61K8/891Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
    • A61K8/893Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone modified by an alkoxy or aryloxy group, e.g. behenoxy dimethicone or stearoxy dimethicone
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q13/00Formulations or additives for perfume preparations
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00Preparations for care of the skin
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00Preparations for care of the skin
    • A61Q19/10Washing or bathing preparations
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q3/00Manicure or pedicure preparations
    • A61Q3/02Nail coatings
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00Preparations for care of the hair
    • A61Q5/02Preparations for cleaning the hair
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00Preparations for care of the hair
    • A61Q5/12Preparations containing hair conditioners
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/02Silicon compounds
    • C07F7/08Compounds having one or more C—Si linkages
    • C07F7/18Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804Compounds having Si-O-C linkages
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11BPRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B9/00Essential oils; Perfumes
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/162Organic compounds containing Si
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/22Carbohydrates or derivatives thereof
    • C11D3/221Mono, di- or trisaccharides or derivatives thereof
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/22Carbohydrates or derivatives thereof
    • C11D3/222Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3703Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/373Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/57Compounds covalently linked to a(n inert) carrier molecule, e.g. conjugates, pro-fragrances
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q1/00Make-up preparations; Body powders; Preparations for removing make-up
    • A61Q1/02Preparations containing skin colorants, e.g. pigments
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q15/00Anti-perspirants or body deodorants
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q9/00Preparations for removing hair or for aiding hair removal
    • A61Q9/02Shaving preparations

Abstract

A consumer product comprises silane-modified oil comprising a hydrocarbon chain selected from the group consisting of: a saturated oil, an unsaturated oil, and mixtures thereof; and at least one hydrolysable silyl group covalently bonded to the hydrocarbon chain. The consumer product further comprises a preservative.

Description

Comprise the consumer products of silane-modified oil
Technical field
Consumer products, its gel comprising silane-modified oil, comprise the granule of silane-modified oil and/or comprise silane-modified oil, and comprise antiseptic.Some consumer products can comprise cosmetic composition, individual cosmetic treatment composition, shaving care composition, home care compositions, Fabrid care composition etc.
Background technology
Silicone elastomer has been widely used in the performance strengthening consumer products, and described consumer products are cosmetic composition, personal care composition, home care compositions and Fabrid care composition such as.Silicone elastomer is generally obtained by SiH polysiloxanes and the another kind of crosslinked hydrosilylation comprising the substituent polysiloxanes of unsaturated hydrocarbons such as vinyl-functional polysiloxanes, or is cross-linked by SiH polysiloxanes and hydrocarbon diene and obtains.Silicone elastomer can be formed under the existence of carrier fluid such as volatile siloxane, obtains cementitious compositions.Alternatively, silicone elastomer can be formed under high solid content, shears subsequently and mixes with carrier fluid, also forms gel or paste-like compositions.
Derivative silicone elastomer also commercialization.Because they are easy to functionalized, silicone elastomer can be customized to provide multiple beneficial effect.This motility is the reason that silicone elastomer is so popularized in consumer product compositions.
Although they have many beneficial effects, when other combination of materials multiple comprised in silicone elastomer and consumer products, can there is preparation challenge in silicone elastomer.Blended characteristic not only depends on the characteristic of single component, the interfacial characteristics also depending on blended form and be present between different mixture component.
Such as, silicone elastomer does not always show the excellent compatibility with organic oil or hydrocarbon (such as non-silicone) oil.Due to the high interfacial tension between silicone elastomer and non-silicone oil, the incompatibility of phase can cause the immiscible blend that is separated.With regard to such as cosmetic foundation, silicone elastomer may not mix the non-silicone oil of desired amount in product, and/or described oil can ooze out from the elastomer finished product, causes unsatisfactory consumer's experience.
Silicone oil and similar components are usually used in preparing multiple consumption product.In recent years, because manufacturer and consumer clearly recognize environmental problem and sustainability problem, therefore the demand of the material with lower content siloxanes is significantly increased.
In addition, the material can sending the beneficial effect similar with those beneficial effects of silicone oil can be the hydrocarbon material that can comprise degree of unsaturation.In general, hydrocarbon ils can have following shortcoming, and they are odorous under many circumstances, and can give taste of the worthless end to the product comprising them.In addition, the hydrocarbon ils with unsaturated part can be easy to oxidized, this can further to product give the worthless end taste because described oxidation can pass in time cause rancid.
Therefore, expect to provide following material, described material can be sent the feature performance benefit of silicone elastomer and have the environmental advantages of material of a large amount of non-silicone fraction, but does not have and decompose or shortcoming that other worthless chemical change such as oxidation Decomposition is associated as become sour.
This type of material should be stable, and is applicable to multiple consumption products application.
Summary of the invention
The invention provides consumer product compositions, its gel comprising silane-modified oil, comprise the granule of silane-modified oil and/or comprise silane-modified oil, wherein said compositions also comprises antiseptic.These oil and/or granule and/or gel can be used for the performance benefits providing multiple expectation with multiple consumption product form.
The invention provides additional aspect, described aspect relates to this type of silane-modified oil, comprises the granule of silane-modified oil and comprises the gel of silane-modified oil.Silane-modified oil and/or the granule comprising silane-modified oil and/or the gel comprising silane-modified oil can comprise the beneficial agent of interpolation; Alternatively, silane-modified oil and/or the granule comprising silane-modified oil and/or the gel comprising silane-modified oil can be used as and thus be considered to beneficial agent.
In one aspect, the invention provides consumer product compositions, it comprises silane-modified oil and antiseptic, and described silane-modified oil comprises: (a) hydrocarbon chain, and the hydrolysable silyl group group of (b) and described hydrocarbon chain covalent bonding.In in specific at one, silane-modified oil comprises:
(i) at least one hydrocarbon chain, described hydrocarbon chain is selected from: fat oil, undersaturated oil and their mixture; With
(ii) the hydrolysable silyl group group of at least one and described hydrocarbon chain covalent bonding.
On the other hand, the invention provides consumer product compositions, it comprises granule containing silane-modified oil and antiseptic.Described granule comprises: (1) has the particle cores on surface between face; (2) the silane-modified oily part on surface between described is attached to.Described granule also can comprise the individual optional aggregation thing of tool.Surface between the face that described silane-modified oil and the optionally polymer diverse location place between face on surface is attached to particle cores.In certain aspects, described granule comprises two kinds or more than the polymer of two kinds and/or characteristic.
On the other hand, the invention provides consumer product compositions, it comprises gel containing silane-modified oil and antiseptic.Described gel pack is containing the product of following material: the oil that (a) is silane-modified; And (b) water, at least some condensation in the hydrolysable silyl group group of wherein said oil, forms other crosslink part in silicone cross-linked between the covalent molecule between oil molecule and/or consumer product compositions.
In specific at one, comprise the gel pack of silane-modified oil containing following product:
A oil that () is silane-modified, described silane-modified oil comprises:
(i) hydrocarbon chain, described hydrocarbon chain is selected from: fat oil, undersaturated oil and their mixture; With
(ii) hydrolyzable silyl-group, itself and described hydrocarbon chain covalent bonding; And
(b) antiseptic
(c) water;
D () at least one comprises the annexing ingredient of at least one hydroxylic moiety
Wherein:
At least some condensation in the hydrolysable silyl group group of i oil that () is silane-modified, thus between the silica-based part of silane-modified oil molecule in crosslinked silane-modified oil, form silicone cross-linked key between covalent molecule; And
(ii) crosslinked silane-modified oil and intermolecular silicone cross-linked key full cross-linked, to form gel.
Present invention also offers the method for the treatment of surface, described method comprises: at least one comprised in the consumer product compositions of silane-modified oil and antiseptic is administered to surface by (a), and water is optionally administered to described surface by (b).In yet another aspect, described method comprises: (a) comprises the consumer product compositions of described silane-modified oil base gel to surface applied, and (b) is optional to described surface applied water.
In specific exploitation, described consumer products comprise delivery apparatus, and described delivery apparatus has at least one first chamber and the second optional chamber.Described first chamber comprises silane-modified oil and optional nonaqueous solvent or carrier, and the second optional chamber comprises water.Any one chamber all can comprise antiseptic.Preferably, described chamber comprises silicyl carburetion, also comprises antiseptic.
Supplementary features of the present disclosure can by following detailed description of the invention, by reference to the accompanying drawings, example and additional claim and become apparent those skilled in the art.
Accompanying drawing explanation
Fig. 1 illustrates the grafting and cross-linking reaction that are associated with the unsaturated triglyceride soybean oil in one aspect of the present invention and unsaturated hydrolyzable silane.
Fig. 2 illustrates the silane-modified oil with particle surface bonding substantially.Illustrate that organo functional silanes's alcohol oil is attached to silica surface.
Fig. 3 illustrates the multiple silane-modified oil with particle surface bonding substantially.Illustrate that organo functional silanes's alcohol oil is attached to silica surface.
Fig. 4 illustrates gel, and described gel pack is containing silane-modified oil and hydroxy-functional inorganic particle and hydroxy-functional organic substance.
Fig. 5 illustrates gel, and described gel pack is containing silane-modified oil and hydroxy-functional organic substance.
Fig. 6 illustrates gel, and described gel pack is containing silane-modified oil and hydroxy-functional inorganic particle.
Detailed description of the invention
The invention provides consumer product compositions, described compositions comprises silane-modified oil, comprise the granule of silane-modified oil and/or comprise the gel of silane-modified oil.These oil and/or granule and/or gel can be used for the performance benefits providing multiple expectation with multiple consumption product form.
The invention provides additional aspect, described aspect relates to this type of silane-modified oil, comprises the granule of silane-modified oil and comprises the gel of silane-modified oil.Silane-modified oil and/or the granule comprising silane-modified oil and/or the gel comprising silane-modified oil can comprise the beneficial agent of interpolation; Alternatively, silane-modified oil and/or the granule comprising silane-modified oil and/or the gel comprising silane-modified oil can be used as and thus be considered to beneficial agent.
In one aspect, the invention provides and comprise silane-modified oil and the consumer product compositions of antiseptic, described silane-modified oil comprises: (a) hydrocarbon chain, and the hydrolysable silyl group group of (b) and described hydrocarbon chain covalent bonding.In in specific at one, silane-modified oil comprises:
(i) at least one hydrocarbon chain, described hydrocarbon chain is selected from: fat oil, undersaturated oil and their mixture; With
(ii) the hydrolysable silyl group group of at least one and described hydrocarbon chain covalent bonding.
Have been found that silane-modified oil of the present invention is generally frowzy and may be suitable for consumer products when not alleviating usually relevant to described silane-modified oil and material composition thereof abnormal flavour.In addition, many response mechanisms for generation of silane-modified oil require that initial raw oil comprises unsaturated hydrocarbon moiety as silylated reflecting point.These unsaturated hydrocarbon moieties also can adversely affect the abnormal flavour be associated with these materials, because unsaturated hydrocarbon moiety can be passed in time, promote the further oxidation of oil, cause rancid.This previous incognizant problem is solved to form consumer products of the present invention by silane-modified oil and antiseptic being mixed by the present invention.
On the other hand, the invention provides consumer product compositions, described compositions comprises granule containing silane-modified oil and antiseptic.Described granule comprises: (1) has the particle cores on surface between face; (2) the silane-modified oily part on surface between described is attached to.Described granule also can comprise the individual optional aggregation thing of tool.Surface between the face that described silane-modified oil and the optionally polymer diverse location place between face on surface is attached to particle cores.In certain aspects, described granule comprises two kinds or more than the polymer of two kinds and/or characteristic.
On the other hand, the invention provides consumer product compositions, described compositions comprises gel containing silane-modified oil and antiseptic.Described gel pack is containing the product of following material: the oil that (a) is silane-modified; And (b) water, at least some condensation in the hydrolysable silyl group group of wherein said oil, forms other crosslink part in silicone cross-linked key between covalent molecule and/or consumer product compositions between oil molecule.
In specific at one, described in comprise silane-modified oil gel pack containing the product of following material:
A oil that () is silane-modified, described silane-modified oil comprises:
(i) hydrocarbon chain, described hydrocarbon chain is selected from: fat oil, undersaturated oil and their mixture; With
(ii) hydrolyzable silyl-group, itself and described hydrocarbon chain covalent bonding; And
(b) antiseptic
(c) water;
D () at least one comprises the annexing ingredient of at least one hydroxylic moiety
Wherein:
At least some condensation in the hydrolysable silyl group group of i oil that () is silane-modified, thus between the silica-based part of silane-modified oil molecule in crosslinked silane-modified oil, form silicone cross-linked key between covalent molecule; And
(ii) crosslinked silane-modified oil and intermolecular silicone cross-linked key full cross-linked, to form gel.
In one aspect, the annexing ingredient that at least one comprises at least one hydroxylic moiety can be selected from hydroxy-functional inorganic particle, hydroxy-functional organic substance and their combination.The example of the functionalized inorganic particle of suitable hydroxyl comprises metal-oxide, such as silicon dioxide, titanium dioxide, aluminium oxide, metallocene and zeolite.The example of hydroxy-functional organic substance comprises oligosaccharide and polysaccharide and derivant such as cellulose, guar gum, starch, cyclodextrin, hydroxypropyl guar gum, hydroxypropyl cellulose, Rhaball Gum CG-M 8M, Polyquaternium-10, dimethiconol, hydroxy-end capped polybutadiene, poly(ethylene oxide), poly(propylene oxide) and poly-(tetramethylene ether) glycol.In specific at one, hydroxy-functional material comprises multiple hydroxy functional group, makes to form bridge between the binding site of multiple silane-modified oil, thus forms gel.
Present invention also offers the method for the treatment of surface, described method comprises: at least one comprised in the consumer product compositions of silane-modified oil and antiseptic is administered to surface by (a), and water is optionally administered to described surface by (b).In yet another aspect, described method comprises: (a) comprises the consumer product compositions of described silane-modified oil base gel to surface applied, and (b) is optional to described surface applied water.
The compositions and methods of the invention can be used for treatment surface such as fabric, yarn fabric, leather, non-woven fabric or weaven goods substrate, fiber, carpet, house decorative material, glass, pottery, skin, hair, fingernail, stone material, masonry, timber, plastics, paper, cardboard, metal, packaging or package component.
In specific exploitation, described consumer products comprise delivery apparatus, and described delivery apparatus has at least one first chamber and the second optional chamber.Described first chamber comprises silane-modified oil and optional nonaqueous solvent or carrier, and the second optional chamber comprises water.Any one chamber all can comprise antiseptic.Preferably, the chamber comprising the silica-based alkymer of first also comprises antiseptic.
As used herein, " oil " refers to any alkyl material, comprises room temperature solid and room temperature liquid.Oil comprises monoglyceryl ester, two glyceride and triglyceride, and fatty acid or their ester or aldehyde.Oil also comprises hydrocarbon, comprises hydrocarbon, aromatic hydrocarbon and comprises the hydrocarbon of both aliphatic series and aromatic fractions.As used herein, " oil " also comprises hydrocarbyl polymers, comprises polyvinyl and their derivant.In addition, " oil " comprises straight chain, side chain or crosslinked polymer.Particularly, described polymer comprises the polymer obtained by one or more ethylenically unsaturated monomers.With regard to object of the present invention, the main chain of the polymer prepared by one or more ethylenically unsaturated monomers is considered to hydrocarbon chain (hydrolyzable silyl-group and described hydrocarbon chain covalent bonding).
As used herein, " undersaturated oil " refers to that each unsaturated oils molecule comprises the oil of at least one aliphatic unsaturated hydrocarbon.Undersaturated oil comprises monoglyceryl ester, two glyceride and triglyceride, and unsaturated fatty acid or their ester.Undersaturated oil also comprises aliphatic unsaturated hydrocarbon.Undersaturated oil can be natural undersaturated, or they can be obtained by other material (such as fat oil) known in the art.With regard to object of the present invention, the unsaturated main chain of the polymer prepared by one or more ethylenically unsaturated monomers is considered to aliphatic unsaturated hydrocarbon (hydrolyzable silyl-group and described hydrocarbon chain covalent bonding).
As used herein, " fat oil " refers to the oil not comprising any aliphatic unsaturated hydrocarbon in oil molecule.Fat oil comprises monoglyceryl ester, two glyceride and triglyceride, and satisfied fatty acid or their ester.Fat oil also comprises saturated hydrocarbon chain.Fat oil can be natural saturated, or they can be obtained by other material known in the art (such as undersaturated oil).With regard to object of the present invention, the saturated main chain of the polymer prepared by one or more ethylenically unsaturated monomers is considered to saturated hydrocarbon chain (hydrolyzable silyl-group and described hydrocarbon chain covalent bonding).
As used herein, " spice " refers to and comprises one or more perfume bases and the material providing fragrance and/or minimizing stench.Those of ordinary skill in the art should be appreciated that single perfume base also can provide fragrance and/or reduce stench.
As used herein, " antiseptic " is referred to and adds in consumer product compositions in case stop-pass any material of crossing growth of microorganism or being decomposed by worthless chemical change.Antiseptic can be naturally occurring or synthesis obtains.
As used herein, " particle benefit agent " refers to any composition in use giving beneficial effect, and wherein said composition is at room temperature solid and is insoluble in product.
As used herein, time in for claim, article such as " one " and " one " are understood to mean one or more or material of describing claimed by right.
As used herein, term " solid " comprises granule, powder, strip and tablet form.
As used herein, term " fluid " comprises liquid, gel, paste and gas product form.
As used herein, term " position " comprises paper products, fabric, clothing, hard surface, hair and skin.
As used herein, term " comprises ", " comprising " and " containing " be nonrestrictive.
Except as otherwise noted, all molecular weight all provide in units of dalton.
As used herein, term " hydrocarbon polymer group " refers to the polymeric groups only comprising carbon and hydrogen.
As used herein, term " siloxy residue " refers to polydimethylsiloxane moieties.
Term used herein " replacement " refers to organic composite or the group of this term of application: (a) becomes unsaturated by cancellation element or group; Or the part of at least one hydrogen involved one or more (i) carbon atom, (ii) oxygen atom, (iii) sulphur atom, (iv) nitrogen-atoms or (v) halogen atom in (b) compound or group substitute; Or (c) (a) and (b) the two.
As alternative hydrogen described in (b) above, the part only comprising carbon atom and hydrogen atom is all hydrocarbon part, and described hydrocarbon part includes but not limited to the combination each other of alkyl, thiazolinyl, alkynyl, alkyl dialkylene, cycloalkyl, phenyl, alkyl phenyl, naphthyl, anthryl, phenanthryl, fluorenyl, sterol radical and these groups and the combination of these groups and polyvalent hydrocarbon radical (such as alkylidene, alkylidene radical and alkylidene).Comprise containing the part of oxygen atom the group comprising hydroxyl, acyl group or ketone group, ether, epoxy radicals, carboxyl and ester as the alternative hydrogen above described in (b).Part as the sulfur atom-containing of the alternative hydrogen above described in (b) comprises acid and acid esters group, sulfide group, mercapto groups and the sulfur keto group of sulfur-bearing.
Part as the nitrogen atom of the alternative hydrogen above described in (b) comprises amino group, nitryl group, azo group, ammonium group, amide group, azido group, isocyanate groups, cyano group and nitrile group.The concrete non-limiting example of this type of nitrogen-containing group is:--NHCH 3,--NH 2,--NH 3+,--CH 2cONH 2,--CH 2cON 3,--CH 2cH 2cH=NOH,--CN,--CH (CH 3) CH 2nCO,--CH 2nCO,--Nphi ,-phiN=NphiOH and ≡ N.
Part as the halogen atom-containing of the alternative hydrogen above described in (b) comprises chloro, bromo, fluoro, iodo group and any preceding sections, and wherein hydrogen or pendant alkyl group are replaced to form stable replacement part by halogen group.The concrete non-limiting example of this type of Halogen group elements is:--(CH 2) 3cOCl ,-phiF 5,-phiCl,--CF 3, and--CH 2phiBr.
Should be appreciated that any above-mentioned part of alternative hydrogen as described in (b) monovalence can replace or mutually replace, to form the monovalence part of hydrogen in another kind of alternative organic compound or group with multivalence replacement by losing hydrogen.
As used herein, " phi " or " ph " represents phenyl ring.
As used herein, the ratio of name SiO " n "/2 represention oxygen atom and silicon atom.Such as, SiO1/2 represents that an oxygen atom is shared between two silicon atoms.Equally, SiO2/2 represents that two oxygen atoms are shared between two silicon atoms, and SiO3/2 represents that three oxygen atoms are shared between two silicon atoms.
Except as otherwise noted, all components or composition levels are all with regard to the active substance part with regard to this component or compositions, do not comprise the impurity in the commercial source that may be present in these components or compositions, such as residual solvent or by-product.
Except as otherwise noted, all percentage ratio and ratio are all by weight.Except as otherwise noted, all percentage ratio and ratio are all based on total composition meter.
Should be appreciated that each the greatest measure limit provided in this manual includes each lower numerical limitation, as this lower numerical limitation is clearly indicated in this article.Each lower limit provided in this manual will comprise each higher limit, as if such higher numerical limitations were expressly written herein.Each numerical range provided in whole description will comprise each the narrower numerical range fallen in this type of wider numerical range, just as this type of narrower numerical range all clearly writes herein.
consumer product compositions
The application provides consumer products, the nursing agent such as comprising silane-modified oil and/or the gel comprising silane-modified oil and/or comprise the granule of silane-modified oil.According to the final use characteristic expected, silane-modified oil can be incorporated in consumer product compositions in any suitable form.Such as, silane-modified oil can precrosslink to form Si-O-Si key.In one aspect, this crosslinked occurs in silane-modified oil and another kind has between the material of oh group (being such as selected from the Si-OH group of silicon dioxide or siloxanes).
Compositions of the present invention can provide beneficial effect, such as soft feeling, feel, wrinkle resistance, hair-conditioning/curl control, color fixative, increase gloss, increases spreadability, dermal sensation and rheological behavior modification (thickening), repellents etc.
As used herein, " consumer products " refer to the product such as baby care product, personal care articles, fabric & nursing at home product, household care (such as, medicated napkin, napkin), feminine care article, health product being generally intended to be used with it by the form of selling or consume.This series products includes but not limited to diaper, bib, cleaning piece, relate to product and/or the method for process hair (people, Canis familiaris L. and/or cat), comprise bleaching, painted, dyeing, nurse one's health, shampoo sends out, shapes, deodorizer and antiperspirant, personal cleansing product, cosmetics, skin care product, comprises cream, emulsion and other local application product for consumer and comprises fine fragrance, and shaving product, relate to process fabric, the product on other surface any in hard surface and fabric extent and/or method, and household care, comprise: Air care product (comprising air freshener and flavor delivery system), Automobile care product, Dish-Washing Products, fabric conditioning product (comprising softening and/or pure and fresh), laundry detergent product, clothes washing and rinsing additive and/or nursing product, hard surface cleaning and/or treatment product (comprising floor and detergent for water closet), and for other cleaning product of consumer or mechanism, relate to product and/or the method for toilet paper, medicated napkin, tissue and/or napkin, tampon and sanltary towel.
As used herein, term " consumer products " and " consumer product compositions " exchange and use.
Compositions of the present invention can be advantageously used in clean and/or treatment compositions.As used herein, term " clean and/or treatment compositions " is the subset of consumer products, and unless otherwise, it comprises beauty care items, fabric and household care products.This series products includes but not limited to, for the treatment of the product of hair (people, Canis familiaris L. and/or cat), comprises bleaching, painted, dyeing, conditioning, shampoo sends out, shapes; Deodorizer and antiperspirant; Personal cleansing product; Cosmetics; Skin care product comprises to be used cream, emulsion and other local application product for consumer and comprises fine fragrance; And shaving goods, for the treatment of the product on other surface any in fabric, hard surface and fabric extent; And household care, comprise Air care product (comprising air freshener and abnormal smells from the patient delivery system), Automobile care product, dishwashing detergent product, fabric-conditioning product (comprising softening and/or pure and fresh), the washing of laundry detergent product, clothes and rinsing additive and/or nursing agent, hard surface cleaning and/or treatment product, comprise general or " heavy duty detergent " detergent of floor and detergent for water closet, graininess or powder type, especially cleaning detergent; The all-purpose detergent of liquid, gel or paste form, especially so-called heavy duty liquid type; Liquid fine fabric detergents; Detergent for washing dishware with hand or light-duty dishwashing agent, those of especially high foaming type; Dishwashing detergent for machine washing, comprises various lamellars, graininess, the liquid and rinse aid type for family and mechanism; Cleaning liquid and disinfectant, comprise antibacterial hand washing type, cleaning rod, collutory, denture cleanser, toothpaste, automobile or carpet detergent, bathroom detergent comprise detergent for water closet; Hair detergent and hair rinses; Bath gels, fine fragrance and bubble bath and metal detergent; And clean adjuvant, such as bleach additive and " decontamination rod " or pretreatment type, the product such as dehydrator with substrate adds paper, dry and wet paper towel and liner, nonwoven substrate and sponge; And all for consumer or/and the spraying of mechanism and mist agent.
Compositions of the present invention can be advantageously used in fabric and/or hard surface cleaning and/or treatment compositions.As used herein, term " fabric " and/or hard surface cleaning and/or treatment compositions " be subset that is clean and treatment compositions, except as otherwise noted, it comprises general or " heavy duty detergent " detergent of graininess or powder type, especially cleaning detergent; The all-purpose detergent of liquid, gel or paste form, especially so-called heavy duty liquid type; Liquid fine fabric detergents; Detergent for washing dishware with hand or light-duty dishwashing agent, those of especially high foaming type; Dishwashing detergent for machine washing, comprises various lamellars, graininess, the liquid and rinse aid type for family and mechanism; Cleaning liquid and disinfectant, comprise antibacterial hand washing type, cleaning rod, automobile or carpet detergent, bathroom detergent comprise detergent for water closet; And metal detergent, fabric conditioning product comprises softening and/or pure and fresh, and it can the form of liquid, solid and/or dehydrator paper; And clean adjuvant such as bleaches additive and " decontamination rod " or pretreatment type, the product such as dehydrator with substrate adds paper, dry and wet napkin and liner, nonwoven substrate and sponge; And spray and mist agent.These series products all that can use all can be canonical form, conc forms or even highly enriched form, and in some aspects, this series products can be even non-water.
In the domestic polishing agent that compositions of the present invention can be advantageously used in floor and table top and cleaning agent.They increase gloss, be easy to sprawl and not with surfacing chemical reaction.Nursing agent in fabric softener contributes to due to their softening performance retaining " brand-new degree ", and their elasticity contributes to making wrinkle smooth.Nursing agent also can strengthen footwear and clean and polishing product.
Compositions of the present invention can be advantageously used in the product of process base type, such as supatex fabric or thin page sanitary tissue products.The non-limiting example of consumer products of the present invention comprises absorbent article, described absorbent article is selected from: towel, wet tissue, surface cleaning wipes, clean fabric cleaning piece, skin cleansing wipes, makeup removing cleaning piece, apply cleaning piece, automobile washing cleaning piece, eyeglass cleaning wipe, packaging material, cleaning wipe, dedusting cleaning piece, packing material, disposable garment, disposable surgical or medical clothes, binder, napkin, toilet paper, facial wipes and wound dressing, baby diaper, training pants, adult incontinence product, feminine care applications, mattress and incontinence pad.In one aspect, absorbent article comprises top flat, egative film or the obstruct hoop crossed by compositions-treated of the present invention.
With the substrate of present composition process by making the substrate of process and pending surface contact, and for the treatment of surface.In one aspect, the described substrate processed can be supatex fabric.In yet another aspect, the described substrate processed can comprise a part for absorbent article.
In one aspect, after described product dried, by the substrate of handled mistake with being less than 1 gram every square metre (gsm), or 0.01 – 10gsm, or 0.01 – 5gsm, or the compositions-treated of the present invention of 0.01 – 2gsm.
Compositions of the present invention can be applied to substrate via any one in multiple device known to persons of ordinary skill in the art.In one aspect, when being applied to substrate, described compositions comprises carrier, and described carrier is selected from water, ethanol, solvent, isopropyl alcohol, surfactant, emulsifying agent and their combination.
silane-modified oil
Comprise (a) hydrocarbon chain according to silane-modified oil of the present disclosure, described hydrocarbon chain is selected from: fat oil, undersaturated oil and their mixture; (b) the hydrolysable silyl group group of at least one and described hydrocarbon chain covalent bonding.Hydrolysable silyl group group generally at the carbon location place, inside along described hydrocarbon chain length, and not at end carbon place (carbon at chain end place relative with ester/acid groups in such as fatty acid/triglyceride), with described hydrocarbon chain covalent bonding.
Silane-modified oil can have the degree of unsaturation of any expectation, can be maybe completely saturated.Degree of unsaturation or saturation can adopt any suitable method to change by those skilled in the art.In addition, hydrocarbon chain can before hydrolysable silyl group radicals covalent bonds is incorporated on it, period or hydrogenation afterwards or dehydrogenation, this depends on and preferably requires and concrete hydrogenation used or method of dehydrogenating.
In one aspect, undersaturated oil and undersaturated hydrolyzable silane is made to react in the presence of radical initiators for the formation of comprising according to the method for silane-modified oil of the present disclosure.Reaction is formed thus has the silane-modified oil with the hydrolysable silyl group group of unsaturated oils molecule covalent bonding.The silane-modified oil of gained can have any silylanizing degree desired by specific products application.In one aspect, silane-modified oil can comprise the hydrolysable silyl group group that the silane-modified oil of average per molecule is less than 1.2 covalent bondings, the silane-modified oil of preferred average per molecule is less than the hydrolysable silyl group group of 1.0 covalent bondings, and the silane-modified oil of preferred average per molecule is less than the hydrolysable silyl group group of 0.8 covalent bonding.In yet another aspect, silane-modified oil can comprise the hydrolysable silyl group group that the silane-modified oil of average per molecule is greater than 1.2 covalent bondings, the silane-modified oil of preferred average per molecule is greater than the hydrolysable silyl group group of 1.5 covalent bondings, and the silane-modified oil of preferred average per molecule is greater than the hydrolysable silyl group group of 2.0 covalent bondings.In yet another aspect, silane-modified oil can comprise the hydrolysable silyl group group of the silane-modified oil of average per molecule about 0.7 to about 5.0 covalent bondings, the silane-modified oil about 0.7 of preferred average per molecule is to the hydrolysable silyl group group of about 2.4 covalent bondings, and the silane-modified oil about 0.7 of preferred average per molecule is to the hydrolysable silyl group group of about 1.6 covalent bondings.In yet another aspect, silane-modified oil can comprise the hydrolysable silyl group group that the silane-modified oil of average per molecule is greater than 5.0 covalent bondings.
Silane-modified oil can compounding in consumer products of the present invention before purification.Described purification can adopt any purified form known to persons of ordinary skill in the art.In one aspect, silane-modified oil is by removing remaining reagent, and the remaining reagent preferably comprising silicon atom carrys out purification.In one aspect, purification comprises preferably under vacuum and/or the temperature higher than ambient temperature (such as 21 DEG C), evaporation of residual reagent.In one aspect, purified silane-modified oil comprises the remaining reagent comprising at least one silicon atom being less than about 10%, preferably be less than the remaining reagent comprising at least one silicon atom of about 5%, preferably be less than the remaining reagent comprising at least one silicon atom of about 1%, be preferably less than the remaining reagent comprising at least one silicon atom of about 0.1%.
Also disclose the method for the oil of cross-linking silane modification.Described method comprises with the silane-modified oil of water crosslinking, thus is hydrolyzed and condensation hydrolysable silyl group group, to form silicone cross-linked key between covalent molecule in silane-modified oil.In one aspect, silane-modified oil can provide with the form of mixtures of crosslinking catalyst (such as titanium catalyst, tin catalyst).
In one aspect, undersaturated oil can derived from the triglyceride be made up of fatty acid ester group, and described fatty acid ester group comprises the unsaturated site of at least one olefinic (such as, the undersaturated oil of at least one aliphatic unsaturated hydrocarbon per molecule jointly; Usually silicone oil, alkoxy end-capped (or other hydrolyzable groups end-blocking) silicone oil or end hydrosilyl carburetion is not comprised).Such as, specific triglyceride molecule can have three aliphatic fatty acid ester group, and wherein at least one has at least one undersaturated carbon-to-carbon double bond.When there is enough degrees of unsaturation in fatty acid ester, monoglyceryl ester and two glyceride also can be used.
Undersaturated oil generally comprises natural oil, such as any undersaturated plant or animal oil or fat; More specifically, term " oil " generally refers to lipid conformation (natural or synthesis), and no matter they are at room temperature generally liquid (i.e. oil) or are at room temperature solid (i.e. fat).The example of unsaturated oils includes but not limited to natural oil such as soybean oil (preferably), safflower oil, Semen Lini oil, Semen Maydis oil, Oleum Helianthi, olive oil, low erucic acid rapeseed oil, Oleum sesami, Oleum Gossypii semen, Petiolus Trachycarpi oil, seed of Papaver somniferum L. powder, Oleum Arachidis hypogaeae semen, Oleum Cocois, Oleum Brassicae campestris, Oleum Verniciae fordii, Oleum Ricini, fish oil, whale oil, Abyssinia's oil (preferably) or their any mixture.
In addition, the vegetable oil of any part hydrogenation or the vegetable oil through genetic modification can also be used.Partially hydrogenated vegetable oil or include but not limited to high oleic safflower oil, high gas oil ratio soybean oil, high gas oil ratio Oleum Arachidis hypogaeae semen, high oleic sunflower oil and high erucic acid rape seed oil (Crambe abyssinica oil) through the example of the vegetable oil of genetic modification.Alternatively or in addition, any undersaturated fatty acid (comprising 10 to 24 carbon or 12 to 20 carbon in such as aliphatic unsaturated hydrocarbon) or its ester (such as comprising the Arrcostab of 1 to 12 carbon atom, hydrocarbon ester) also can be used as according to undersaturated oil of the present disclosure individually or as mixture.The iodine number of undersaturated oil preferably in the scope of about 40 to 240 (such as about 80 to 240, about 120 to 160).When use there is lower iodine number oily time, the hydrolysable silyl group group of low concentration will be obtained in silane-modified oil.
Undersaturated hydrolyzable silane comprises the silicon base compound of the hydrolyzable functional group with unsaturated hydrocarbons residue and at least one and silicon atom bonding.The example of suitable unsaturated hydrolyzable silane is represented by formula I:
R " msiR 4-(n+m)x n[formula I]
In formula 1, i () X is hydrolyzable functional group, (ii) R is end group or atom, (iii) R " be undersaturated hydrocarbon residue; and (iv) n is the integer in 1 to 3 scope; m is the integer in 1 to 3 scope, and n+m<=4.The value of n is preferably 2 or 3 (more preferably 3), thus in crosslinked silane-modified oil, allows more than one siloxane bond and contribute to forming networking gelatin polymer.In general, undersaturated hydrolyzable silane comprises single carbon-to-carbon degree of unsaturation (namely m is 1), makes silane and undersaturated oily covalent bonding, and without any worthless crosslinked between undersaturated oil molecule.But in some respects, undersaturated hydrolyzable silane is polyunsaturated (such as m is 2 or 3, and/or R " be polyunsaturated).Preferred undersaturated hydrolyzable silane comprises vinyltrimethoxy silane, VTES, vinyltriacetoxy silane, allyl dimethyl base acetoxylsilane, pi-allyl three isopropoxy silane and allyl phenyl hexichol TMOS.R ", R and X can select independently of one another, and the concrete example of each group is shown in hereinafter.
The example of hydrolyzable functional group X comprises alkoxyl (such as methoxyl group, ethyoxyl), carboxylic oxygen base (such as acetoxyl group) or aryloxy group.Optionally, X can be halogen such as chlorine or bromine, but halogen is less preferred because they cause be hydrolyzed time strong acid formation, described acid is preferably neutralized any fatty acid ester (such as, the triglyceride ester bond) saponification prevented in oil.Therefore, in some respects, hydrolyzable functional group (or hydrolysable silyl group group) does not comprise halogen.Most preferably, X is methoxyl group and/or acetyloxy group.This one type of silane is normally available, and their preparation method is known.Preferably wherein there is the silane of three hydrolyzable groups, such as vinyltrimethoxy silane or vinyltriacetoxy silane.
End group R is preferably hydrogen, saturated hydrocarbyl group, saturated clicyclic hydrocarbon group, aromatic hydrocarbon group, heterocyclohydrocarbon group or their combination.Hydrocarbyl group generally comprises 1 to 30 carbon atom (such as 1 to 10 carbon atom, 1 to 6 carbon atom).Such as, R can be the aromatic yl group of hydrogen, saturated alkyl hydrocarbon group, the saturated alkyl hydrocarbyl group of replacement, aromatic yl group or replacement.Alkyl group can be any hydrocarbon of the carbon atom comprising straight or branched configuration.Alkyl/aryl group can be the hydrocarbon of hydrocarbon or replacement, and wherein substituent group comprises hetero atom, halogen, ether, aldehyde, ketone etc.Preferred alkyl group is methyl, ethyl and fluoropropyl group.But preferred at one in, n is 3, m is 1, and end group R is not present in undersaturated hydrolyzable silane.
Undersaturated hydrocarbon residue R " preferably comprises 2 to 30 carbon atoms (such as 2 to 14 carbon atoms, 2 to 6 carbon atoms).In general, undersaturated hydrocarbon residue R " is monounsaturated; But R " can be polyunsaturated (such as dialkylene group).In one aspect, R " unsaturated functional group be positioned at R " end (i.e. R " is CH 2=CH--R '--, wherein R ' is for comprising the hydrocarbon residue of 0 to 12 carbon atom), to promote that undersaturated hydrolyzable silane grafts on undersaturated oil.The aryl moiety that hydrocarbon residue preferably includes alkyl, the alkyl of replacement, aryl or replaces, such as methyl, ethyl, propyl group and phenyl (such as CH 2--CH-ph-).Most preferably, R " is vinyl (CH 2=CH--) or pi-allyl (CH 2=CH--CH 2--) group.
oily is silane-modified
Any suitable method can be adopted to prepare silane-modified oil.In one aspect, utilize undersaturated oil, regulate the relative quantity of undersaturated oil and undersaturated hydrolyzable silane according to specific graft reaction condition (such as, temperature, response time, radical initiator).In some respects, before graft reaction, the content of undersaturated hydrolyzable silane is relative to undersaturated oily molar excess, the mol ratio of such as undersaturated hydrolyzable silane and undersaturated oil is about 1 to about 20, about 2 to about 10, about 3 to about 8, or in about 4 to about 6 scopes.With regard to some application, expect that the undersaturated oil of per molecule (such as fatty acid glyceryl ester) has at least 1 molar reactive silyl-group reactive hydrolysable silane groups of undersaturated oily covalent bonding (namely with), to guarantee to be in or higher than completely crosslinked under gel point.With regard to other application, when expecting that undersaturated oil is not linked in gel network at least partially, the undersaturated oil of per molecule can be used to be less than the reactive silyl-group of 1 mole.
According to the application expected, the amount of the uncrosslinked undersaturated oil stayed in the composition after crosslinked can be different.If use excessive unsaturated hydrolyzable silane, (namely (1) does not comprise the undersaturated oil molecule of hydrolysable silyl group group to leave minimum uncrosslinked undersaturated oil in the composition after being then cross-linked, or (2) comprise the undersaturated oil molecule of hydrolysable silyl group group, the non-hydrolyzing/condensing of described hydrolysable silyl group group and form silicone cross-linked key with another hydrolysable silyl group group).But if use the undersaturated hydrolyzable silane of relatively low amount, then a part of undersaturated oil will not be crosslinking in gel network, and maintenance is dissociated, be tending towards leaching/flowing out from crosslinked compositions.
After graft reaction, all or at least partially undersaturated oil molecule there is at least one hydrolysable silyl group group via aliphatic unsaturated hydrocarbon and its covalent bonding, this depends on desired final use application.In certain aspects, there is no that uncrosslinked undersaturated oil is present in crosslinked compositions and/or can leaches from crosslinked compositions.Such as, relative to the primary quantity of undersaturated oil, the uncrosslinked/oil that can leach can be about 5 % by weight or lower (such as about 2 % by weight, 1 % by weight, or 0.1 % by weight or lower).In numerous applications, this type of is not exclusively crosslinked is worthless, and can cause and stain relevant problem to the region around one or more point of application, the not best performance relevant to adhesiveness, water-resistance and/or aesthetic property and problem.In other applications, this type of incomplete being cross-linked may be favourable, such as, when being present in the uncrosslinked undersaturated oil experience subsequent process in crosslinking mixture to change the performance of mixture further and to form.
radical initiator
In one aspect, radical initiator contributes to undersaturated hydrolyzable silane to the graft reaction (such as via the undersaturated aliphatic chain of undersaturated oil molecule) on undersaturated oil.The usually known any radical initiator in this area is all applicable, wherein the preferred thermal initiator producing free radical when heating.Example includes but not limited to organic peroxide such as benzoyl peroxide, two tert-butyl peroxy compounds, 2, 5-dimethyl-2, 5-bis-(tert-butyl peroxy base) hexane, two (o-methyl-benzene formoxyl) peroxide, two (methyl benzoyl) peroxide, two (to methyl benzoyl) peroxide, or similar monomethyl benzoyl peroxide, two (2, 4-dimethylbenzoyl) peroxide, or similar dimethylbenzoyl peroxide, diisopropylbenzyl peroxide, tert-butyl group 3-isopropenyl cumyl peroxide, 4, 4-bis-(tert-butyl peroxy base) butyl valerate, two (2, 4, 6-trimethylbenzoyl) peroxide, or similar trimethylbenzoyl peroxide.
Radical initiator causes with the part of the reactive hydrolysable silyl group group of undersaturated oily covalent bonding more, and make crosslinked after there is the risk minimization of imperfect network, there is (namely noncrosslinking) undersaturated oil molecule that imperfect network enables to dissociate and be diffused into outside main body.The diffusion couple gel network self of this type of unreacted unsaturated oils molecule automatic network and the physical characteristic of peripheral region have adverse influence.
Add the initiator of any Sq, to guarantee that resulting composition is cross-linked by being grafted on undersaturated oil by enough hydrolysable silyl group groups.Relative to the weight of undersaturated oil ingredient, the consumption of initiator is preferably about 0.1 % by weight to about 10 % by weight (such as about 0.2 % by weight to about 5 % by weight or about 0.5 % by weight to about 2 % by weight).
Preferably, radical initiator is for being substantially free of or not containing in the reactant mixture of antioxidant and/or peroxide scavenger.In some cases, antioxidant and/or peroxide scavenger (such as tert-butyl group Jiao property catechol, Yoshinox BHT, butylated hydroxyanisol, hydroquinone) are joined unsaturated silane, to stop unsaturated silane spontaneous polymerization.But, under without antioxidant and/or peroxide scavenger situation, use radical initiator, promote silylanizing graft reaction, but also reduce the speed of inadvisable side reaction.In addition, in the various exemplary formulation prepared and analyze, do not observe the spontaneous polymerization of unsaturated silane.
bonding
Any suitable bonding method can be used herein.Such as, in one aspect, implementing graft reaction is included in airtight flask with the proper method of the silane-modified oil forming miosture curable, preparation feedback mixture under inertia (such as nitrogen) atmosphere, described reactant mixture comprises the every 5 moles of undersaturated hydrolyzable silanes of undersaturated oil of about 1 mole, and the peroxide initiator of about 1 % by weight (relative to undersaturated oil).Reactant mixture should be substantially free of water to prevent premature hydrolysis and/or silicone cross-linked (such as fully anhydrous with the time based on reaction avoiding reaction, ambient temperature, pH etc. available).Such as, be pumped in 2LParr reactor by reactant mixture under nitrogen envelope, described reactor purges about 5 minutes to guarantee dry atmosphere with drying nitrogen.Parr reactor (purchased from ParrInstrumentCompany (Moline, Ill., USA)) is equipped with mechanical agitator, sample tap and thermocouple well.Then peripheral control unit is used to regulate temperature of reactor, and heating blends, stir with 200rpm simultaneously, so that mixed reactant, and even heat is distributed in whole reactor.
Typical reaction temperature is between about 100 DEG C to about 350 DEG C.With regard to conventional vinyl and unsaturated hydrolyzable silane, reaction temperature is in the higher-end point (such as, about 200 DEG C to about 350 DEG C, or about 200 DEG C to about 300 DEG C) of scope usually.But, " be aromatic yl residue (such as CH as unsaturated hydrocarbons residue R 2=CH-ph-) time, lower reaction temperature can be suitable (such as, about 100 DEG C to about 200 DEG C, or about 100 DEG C to about 180 DEG C).Because many unsaturated hydrolyzable silanes have the boiling point lower than reaction temperature, need careful to guarantee that reactor can bear the pressure accumulated between the reaction period.At the end of reaction, turn off heat, make silane-modified oil cooling to room temperature.Then by simply evaporating, unsaturated for excessive unreacted hydrolyzable silane is removed from product, or stay in product.By sample is placed about 20-30 minutes being held in the heat under 160 degrees Celsius-weight analysis instrument (TGA), measure the amount of (i.e. covalent bonding) and the unreacted hydrolyzable silane reacted in oil.Any unreacted hydrolyzable silane volatilizees from product, is recorded as the loss in weight in TGA.By the loss in weight of volatile part (i.e. unreacted silane) being deducted from the initial weight of the unsaturated hydrolyzable silane reactant mixture, calculate the concentration of the silane of covalent bonding.
In yet another aspect, silane-modified oil comprises straight chain, side chain or crosslinked polymer, and described polymer comprises one or more silanol and/or hydrolyzable siloxy residue.Particularly, polymeric material comprises addition polymers, and described addition polymers is obtained by one or more ethylenically unsaturated monomers and the monomer copolymerization comprising silanol or hydrolyzable siloxy residue.
The polymer that one class is suitable for comprises and uses suitable initiator or catalyst, is polymerized obtained those, such as United States Patent (USP) 6,642 by ethylenically unsaturated monomers, disclosed in 200 those.Suitable polymer can be selected from by being polymerized the obtained synthetic polymer of one or more monomers, and one or more monomers described are selected from: acrylic acid N, N-dialkyl aminoalkyl ester, methacrylic acid N, N-dialkyl aminoalkyl ester, N, N-dialkylaminoalkyl acrylamide, N, N-dialkyl aminoalkyl Methacrylamide, quaternized acrylic acid N, N dialkyl aminoalkyl ester, quaternized methacrylic acid N, N-dialkyl aminoalkyl ester, quaternary ammonium N, N-dialkylaminoalkyl acrylamide, quaternary ammonium N, N-dialkyl aminoalkyl Methacrylamide, methacryiamidopropyl-pentamethyl-1,3-propylene-2-alcohol-dichloride ammonium, N, N, N, N ', N ', N ", N "-seven methyl-N "-3-(1-oxo-2-methyl-2-acrylic) aminopropyl-9-oxo-8-azo decane-Isosorbide-5-Nitrae, 10-tri-chlorination three ammonium, vinylamine and derivant thereof, allylamine and derivant thereof, vinyl imidazole, quatemized vinylimidazol and poly (dially dialkyl) ammonium chloride, N, N-dialkylacrylamides, Methacrylamide, N, N-dialkyl methacrylamides, acrylic acid C 1-C 12arrcostab, acrylic acid C 1-C 12hydroxy alkyl ester, acrylic acid poly alkylene glycol ester, methacrylic acid C 1-C 12arrcostab, methacrylic acid C 1-C 12hydroxy alkyl ester, methacrylic acid poly alkylene glycol ester, styrene, butadiene, isoprene, butane, isobutene., vinyl acetate, vinyl alcohol, vinyl formamide, vinyl acetamide, vinyl alkyl ethers, vinylpyridine, vinyl pyrrolidone, vinyl imidazole, caprolactam, acrylic acid, methacrylic acid, maleic acid, vinyl sulfonic acid, styrene sulfonic acid, acrylamido propyl group methanesulfonic acid (AMPS) and salt thereof.Described polymer can optionally through use Branching and cross-linking monomer branching or crosslinked.Branching and cross-linking monomer comprises ethylene, diacrylate diol ester, divinylbenzene and butadiene.Preferably, described polymer comprises and is less than 8,000 by polymerizable molecular amount, preferably between 500 and 8, and the synthetic polymer that the isobutene. between 000 is obtained.
In one aspect, the monomer comprising silanol or hydrolyzable siloxy residue comprises the monomer with following structure:
Wherein each R is independently selected from hydrogen, C 1to C 12alkyl and C 1to C 12the alkyl group replaced.Each X comprises the divalent alkylene groups comprising 2-12 carbon atom.In one aspect, each divalent alkylene groups independently selected from
Each R 1comprise the divalent alkylene groups comprising 2-12 carbon atom.In one aspect, each divalent alkylene groups is independently selected from-(CH 2) s-, wherein s is the integer of 2 to 8 or 2 to 4; – CH 2– CH (OH)-CH 2– He – CH 2– CH 2-CH (OH) –.Each R 2be selected from OH, C 1-C 8alkoxyl and C 1-C 8alkyl, and each R 3be selected from OH and C 1-C 8alkoxyl.In one aspect, R 3be selected from OH and methoxyl group, ethyoxyl or propoxy group.
silane-modified oil
According to desired final use characteristic, silane-modified oil can have different degrees of unsaturation.In addition, according to desired final use characteristic, silane-modified oil can have the different degrees of branching, aromaticity, molecular weight, chain length, heteroatom functionalized degree or other possible modification any.
As mentioned above, can before grafting process, period or afterwards, change degree of unsaturation.Silane-modified oil can have be present in silane-modified oil be more than or equal to zero double bond, or one or more double bond.Such as, if the reaction by needing to exist double bond is carried out further modification by silane-modified oil, then it is favourable that silane-modified oil comprises a large amount of double bonds.In yet another aspect, the degree of unsaturation of silane-modified oil remains on minima, but in other side, according to the final use application of expection, degree of unsaturation can be uncorrelated.
Such as, in one aspect, silane-modified oil has the degree of unsaturation substantially similar with the degree of unsaturation of undersaturated oil.The inadvisable coupling reaction that similar degree of unsaturation represents between undersaturated oily carbon-to-carbon double bond is minimum, promotes that unsaturated hydrolyzable silane is to the graft reaction on unsaturated oils chain simultaneously.Inadvisable coupling reaction (i.e. " superimposed " reaction) between undersaturated oil molecule is tending towards the molecular weight increasing undersaturated oil, also reduces the available sites of unsaturated hydrolyzable silane grafting simultaneously.The minimizing of available graft site is tending towards obtaining superimposed undersaturated oil molecule further, and it does not exist in any hydrolyzable silane functional group situation, leaches from crosslinked compositions inadvisablely.
Degree of unsaturation can be represented by any one in multiple method expediently.Such as, (such as via NMR spectrographic method) can be measured and the sum of carbon-to-carbon double bond in more initial undersaturated oil and silane-modified oily both products.In certain aspects, undersaturated hydrocarbon chain can retain its carbon-to-carbon double bond, even if the position of double bond changes due to graft reaction.Alternatively, the feature of degree of unsaturation can be iodine number (such as by the iodine number of material consumption, such as by ASTMD1959, ASTMD5768, DIN53241 or equivalent processes measure).
Depend on the final use application of expectation, the relative reservation of the unsaturated characteristic in silane-modified oily product is also expressed by its viscosity, and it can keep similar or can be different from that of reactant oil used.Such as, when using low viscosity vegetable oil as undersaturated oil, silane-modified oily product can have similar low viscosity, and this is conducive to forming level and smooth continuous print film when depositing as coating.In other applications, can expect viscosity adjustment to obtain higher or lower, this depends on desired final use.
Silane-modified oil can characterize further in the concrete structure of one or more hydrolysable silyl group group, as represented by formula II:
--SiR mr 3-(n+m)x n[formula II]
In formula II, X with R can represent the hydrolyzable functional group identical with formula I and end group/atom.In formula II, n is (preferably 3) in 1 to 3 scope, and m is in 0 to 2 scope, and n+m<=3.Due to hydrolysable silyl group group and the undersaturated oily covalent bonding of formula II, therefore R " can the unsaturated hydrocarbons residue of representative formula I or the graft reaction product of unsaturated hydrocarbons residue.Such as, when unsaturated hydrolyzable silane be polyunsaturated and/or with more than one aliphatic unsaturated hydrocarbon covalent bonding, R " can represent vinyl groups (CH 2=CH--) or vinyl groups Vinyl Graft product (--CH 2cH 2--).In general, hydrolysable silyl group group is via representing the R linking group R of graft reaction product " " ' and aliphatic unsaturated hydrocarbon covalent bonding.In this case, directly and the hydrolysable silyl group group of aliphatic unsaturated hydrocarbon covalent bonding (namely via linking group R " ') can be represented by formula IIa:
--R " ' SiR " mr 3-(n+m)x n[formula IIa]
In one aspect, silane-modified oil can be particle form.Described granule comprises: (1) has the particle cores on surface between face; (2) the silane-modified oil on surface between described is attached to; With optional (3), there is the polymer of certain characteristic.Surface between the face that silane-modified oil and the optional polymer diverse location place between face on surface is attached to particle cores.In certain aspects, described granule comprises two kinds or more than the polymer of two kinds and/or characteristic.
particle cores
According to desired attribute, any suitable particle cores can be used.In one aspect, particle cores is the inorganic particle comprising hydroxy functional group on the surface between face.In some cases, nano-particle can be used alone as particle cores, or is used as particle cores as agglomerate.As used herein, term nano-particle (single or as aggregation) refers to that its longest dimension is less than the granule of 500 nanometers.In one aspect, nano-particle is 1 to 500 nanometer, in yet another aspect, is 150 to 250 nanometers, and in yet another aspect, nano-particle is 50 to 100 nanometers.
Desired beneficial effect can instruct the particle cores selecting to be used to any concrete consumer product compositions.Such as, granule (or particle agglomerates) such as silicate granules (such as pyrogenic silica), aluminium silicate, metal-oxide (such as zinc oxide, titanium dioxide) can be used as particle cores.
Can be used for other non-limiting example of the material forming particle cores comprising normal complexion non-staining pigment, coated interference pigment, inorganic powder and their combination.These granules can be such as sheet shape, spherical, longilineal or aciculiform or random shape, surface-coated or uncoated, porous or atresia, electrically charged or uncharged.Muscovitum, zeolite, Kaolin, silicon dioxide, boron nitride, Talcum, aluminium oxide, barium sulfate, calcium carbonate, glass and their mixture that concrete material can include but not limited to bismuth oxychloride, sericite, Muscovitum, cross by barium sulfate or other material processed.
Other pigment that can be used in the present invention can provide color mainly through optionally absorbing the visible ray of specific wavelength, and comprise inorganic pigment, organic pigment, and their combination.The example of this type of available inorganic pigment comprises ferrum oxide, ammonium ferrocyanide ferrum, manganese violet, ultramarine blue and chromium oxide.Inorganic white pigment used in the present invention or leuco-pigment, such as TiO 2, ZnO or ZrO 2commercially available from multiple source.An example of suitable particulate material comprises purchased from U.S.Cosmetics (TRONOXTiO 2series, SAT-TCR837, rutile TiO 2) material.Especially the preferably charged dispersion of titanium dioxide, as United States Patent (USP) 5,997, disclosed in 887.
Specific pigment that is coloured or colourless non-interfering type has 1nm to 150,000nm, or 10nm to 5,000nm, or the primary average particle size of 20nm to 1000nm.The mixture with varigrained identical or different pigment/powder also can be used for herein (such as, will have the TiO of about 100nm to about 400nm primary particle size 2with there is about 10nm to the TiO of about 50nm primary particle size 2be incorporated in together).
surface between face
Between the face of particle cores surface can be located immediately on the surface of particle cores self, if or particle cores used be coating particle cores, the one or more layers above particle cores can be positioned at.When particle cores comprises multiple granule, between face, surface can extend across multiple particle surface.
surface attachment between face
The oil molecule that at least one is silane-modified, and optionally one or more polymer be attached to particle cores at difference place face between surface.As used herein, " attachment " can comprise any suitable means for attachment, such as bonding (such as covalency, ion) or absorption (such as Van der Waals force, hydrogen bond etc.), this depends on the desired final response of consumer product compositions.
In one aspect, block copolymer is used.There is polymer that is identical or relative nature can be incorporated in single block copolymer.At single or multiple somes places, block copolymer can be attached to core.
One or more polymer have chemistry and/or physical characteristic: the characteristic of optional at least one polymer is relative with the characteristic of another kind of polymer.The characteristic of polymer also can or alternatively relative with the characteristic of silane-modified oil.The example of characteristic and corresponding relative nature can include but not limited to: hydrophobicity and hydrophilic; Acid and alkaline; And anion with cationic.
The characteristic of one or more polymer is relative with the characteristic of other polymer or relative with the characteristic of silane-modified oil, enables gained granule adapt to its environment.Such as, when affecting the parameter change of concrete property, the characteristic of the first polymer will show, and the impact of the first polymer will be occupied an leading position compared to the relative nature of the second polymer.Such as, the change of solvent polarity can trigger conformational change in polymeric chain, causes more hydrophobic propertys or water-wet behavior to show.Other change can comprise pH, water content, humidity, temperature, solvent, electrolyte concentration, magnetic field, radioactive exposure etc.In specific at one, polymer has a multiple instead of character, thus responds to multiple stimulation (both such as solvent polarity and temperature).
In consumer product compositions, comprise granule therefore can cause following advantage, such as, but not limited to hydrophobic material uneven surface can surface on improvement and deposit uniformly.Such as, these hydrophobic materials deposit in hair surface and change surface energy.In addition, hydrophobic material is formulated in hydrated matrix (such as carrier) and can more easily completes.Otherwise, hydrophilic material is formulated in non-aqueous matrix and also can more easily completes.In addition, environment change can be conducive to removing of granule.
Product type, desired characteristic, stimulating factor and substrate used are depended in the selection of polymer type, content and ratio.In general, expect can in various substrate delivery of particles, retain their stability to agglomeration/flocculation and sedimentation.Such as, relatively large polymer can be selected to reach the stable of entropy.In one aspect, described polymer has the molecular weight being greater than 500, and in yet another aspect, described molecular weight is greater than 15, and 000.In specific at one, described polymer has the molecular weight of 1000 to 300,000.In hydrated matrix, the existence of hydrophilic polymer intermediate ion group will provide additional flocculation/aggregation stability.
In specific, hydrophobic polymer can include but not limited to, the polystyrene fluoridized, polystyrene, polyolefin (and functionalized polyolefin, the such as hydroxy derivatives of cyanide, halogenide, ester, ketopyrrolidine, carboxylic acid, carboxylate, hydroxyl, carboxylate, amide, amine, glycidyl derivatives etc.), polydiene, PDMS and functionalized PDMS, polybutylene oxide, poly(propylene oxide)
, and alkyl derivative and their combination.
In specific, hydrophilic polymer can include but not limited to, polyacrylate (and ester), other functionalized polyolefin, (such as PVA (polyvinyl alcohol and ester), PVA ether, PVP (vinyl pyrrolidone), vinyl cyanide, phosphate ester, phosphonate ester, sulfuric ester, sulphonic acid ester etc.), polymine and other polyamine, Polyethylene Glycol and other polyethers, poly-(maleic anhydride of styrene), polyester, polyureas, polyurethane, Merlon, polyacrylamide, sugar and polymer analog, chitosan, with their derivant and their combination.
In order to have sane response performance (when stimulating rapidly and effective performance of handoffs), the conformational flexibility of polymer is important.Therefore, lower glass transition temperatures is desirable.
When being attached mechanism and being absorption, in order to reach effective attachment under proper condition, it may be favourable for polymer existing multiple granule affinity group.
Fig. 2 illustrates the silane-modified oil with particle surface bonding substantially.Illustrate, organo functional silanes's alcohol oil is attached to silica surface.
prepare the method for granule
In yet another aspect, the invention provides the method for the preparation of the granule in consumer product compositions.Described method comprises: (1) provides the granule with surface between face, and (2) make silane-modified oil (optionally having at least one characteristic) be attached to surface between described; And optional (3) make to have the polymer of identical or relative nature or their combinations are attached to surface between described.Step (2) and (3) can any suitable order be carried out, and comprise overlap or simultaneously, this depends on concrete polymer and desired attachment method.Comprise block copolymer in, the first block can have the first characteristic, and the second block can have the second characteristic; Described characteristic can be identical or relatively or be their combination.
In general, described granule is by following preparation/manufacture: use existing particulate feed material as preformed particle cores (pigment, implant etc.), and make the functional group on their surfaces and polymer reaction, or polymeric material is adsorbed on them on the surface.
Alternatively, the result that granule can be used as the polyreaction of soluble/emulsible monomer or macromonomer manufactures.Resulting polymers/copolymer not only can form real core, and can form the polymer of attachment, provides response characteristic.In addition, polyreaction can be carried out under granule (such as inorganic pigment) exists, and granule can serve as additional core material.
Form granule via polyreaction, simple, quick and economic method can be provided.Such as, can the dimethoxy siloxane macromer of initiator, ethylene end-blocking and such as comprise alkene poly(ethylene oxide) existence under utilize and comprise the aqueous emulsion polymerization reaction of the monomer of at least one ethylene group.Use surfactant, siloxane macromer can together with other monomer emulsifying in water-bearing media, to determine that it take part in polyreaction.After polymerization, the dispersions obtained polymer beads (latex) comprising the macromonomer with attachment.The inorganic particle (such as titanium dioxide, zinc oxide, silicon dioxide etc.) added in reactant mixture before polymerization or other polymer beads also participate in latex particle.
Typical emulsion polymerisation monomer can comprise methyl methacrylate, acrylonitrile, ethyl acrylate, Methacrylamide, styrene etc.More hydrophilic monomer such as acrylic acid and methacrylic acid also can copolymerization.The example of PDMS macromonomer can comprise the polydimethylsiloxane of the polydimethylsiloxane of ethenyl blocking, vinyl methyl siloxane-dimethylsiloxane copolymer and methacryloxypropyl end-blocking.The example of polar macromonomer can comprise the polyoxyethylene ester of undersaturated fatty acid, the polyoxyethylene ether of fatty alcohol, the polyaziridine of ethenyl blocking and methacrylic acid 2-(dimethylamino) ethyl ester.
When attempting carrying out dispersion polymerization in the organic solvent replacing water, similar result can be obtained.The typical solvent that can be used in this free radical dispersion polymerization comprises methyl ethyl ketone and isopropyl alcohol.
When by inorganic particle (such as titanium dioxide, zinc oxide or silicon dioxide) for aqueous reaction mixture in, granule unsaturated fatty acid polyoxyethylene ester or fatty alcohol-polyoxyethylene ether encapsulating, react with PDMS macromonomer subsequently, can be the another kind of approach producing similar response structure.
be cross-linked and gel
According to the application of desired final use, silane-modified oil can before being applied to substrate, period or be cross-linked afterwards.Such as, silane-modified oil directly can be applied to surface, maybe it can be processed further, to form crosslinked gel network or reactive particle before surface applied.
Silane-modified oil crosslinked by realizing with hydroxy-functional substance reaction, described hydroxy-functional material comprise inorganic hydroxy-functional granule or organic hydroxylic functionalized species or the two.
Silane-modified oil is by being exposed to water; thus hydrolysable silyl group group is hydrolyzed into silanol; and subsequently by described silanol condensation with in silane-modified oil; or between silane-modified oil and hydroxy-functional material (such as inorganic particle or organic substance, or both), form silicone cross-linked key between covalent molecule be cross-linked.In one aspect, crosslinked water represents atmospheric water (in such as air the water of about 5 volume % at the most, about 0.5 volume % is to about 5 volume %, about 1 volume % to about 2 volume %, or the relative humidity of about 20% to about 100%) simply.Therefore, simply the compositions comprising silane-modified oil is applied to exposure substrate in an atmosphere, and silane-modified oil is cross-linked gradually along with atmospheric water hydrolysis hydrolysable silyl group group.Cross-linked speed depends on the concentration of hydrolysable silyl group group, relative humidity, temperature and is applied to the layer thickness of silane-modified oil of substrate.Crosslinking temperature can be ambient temperature (such as about 25 degrees Celsius).Alternatively or in addition, silane-modified oil can remain on controlled temperature or be heated to controlled temperature, such as at the most about 80 degrees Celsius, or about 25 degrees Celsius to about 60 degrees Celsius.In addition, pH can affect cross-linked speed.Such as, promote to be cross-linked by forming more acid environment, wherein silyl-group is easier to be hydrolyzed into silanol, and it forms cross-bond with after-condensation.
Known crosslinking catalyst can be used to promote cross-linked speed further, the reaction (being commonly referred to as " promoter " in this area) of the hydrolyzable silane caused to promote moisture.The example of appropriate catalysts comprises titanium catalyst such as aphthenic acids titanium, butyl titanate, tetraisopropyl titanate, metatitanic acid two-(acetylacetone based)-diisopropyl ester, metatitanic acid four-2-Octyl Nitrite, tetraphenyl titanate, triethanol amine titanate, organic siloxy titanium compound (such as United States Patent (USP) 3,294, those described in 739) and β-dicarboxyl titanium compound (such as U.S. Patent No. 3,334, those described in 067), two sections of patents are incorporated herein by reference, to illustrate titanium catalyst.Alternatively, organic metal stannum condensation cross-linking catalyst can be used to promote cross-linked speed.The example of carboxylic acid stannum condensation cross-linking catalyst comprises dibutyl tin laurate, dibutyltin diacetate, tin dilaurate dioctyl tin, tin octoate or their mixture.Preferred catalyst comprises butyl titanate, tetraisopropyl titanate and metatitanic acid two-(acetylacetone based)-diisopropyl ester.Relative to the weight of silane-modified oil, the amount of crosslinking catalyst is preferably in about 0.2 % by weight to about 6 % by weight (such as about 0.5 % by weight to about 3 % by weight) scope.When it is present, crosslinking catalyst preferably provides as the mixture of the oil silane-modified with moisture curable, makes two kinds of components can be applied to surface in single operation.
In one aspect, crosslinked silane-modified oil can between its covalent molecule silicone cross-linked key concrete structure in characterize further, such as, as represented by formula III:
--R " '--Si (Y) 2--O--Si (Y) 2--R " '--[formula III]
In formula III, Y part can represent independently--OH (that is, hydrolysis but the silanol of not condensation),--R,--R ",--O--Si (Y) 2--R " '--and their combination.The recursive definition of Y shows, silicone cross-linked key can be branching, but needs not to be 2-silicon cross-bond.R-portion can represent the end group/atom identical with formula 1, and R " partly can represent the unsaturated hydrocarbons residue identical with formula II and graft reaction product thereof." ' part represents the linking group identical with formula II to R, and therefore general expression has the hydrocarbon residue of 2 to 30 carbon atoms (such as 2 to 14 carbon atoms, or 2 to 6 carbon atoms).Particularly, R " ' part be at two ends of intermolecular silicone cross-linked key and oily aliphatic unsaturated hydrocarbon covalent bonding, thus by least two silane-modified covalently bound linking groups together of oil molecule.In one of crosslinked oil, (i) undersaturated oil comprises soybean oil; (ii) Y part represents--OH,--O--Si (Y) independently 2--R " '--and their combination; And (iii) R " ' part represents independently--CH 2cH 2--,--CH 2cH 2cH 2--and their combination.
On the other hand, the crosslinked of silane-modified oil can be realized by bridging by hydroxy-functional inorganic particle or hydroxy-functional organic substance or both.
In crosslinked silane-modified oil, substantially all oil molecules can be cross-linked at least one other oil molecule via intermolecular silicone cross-linked key.In addition, the leaching of non-silylanizing oil molecule is limited.After crosslinked, silane-modified oil preferably has the gel content at least about 70% (such as at least about 80%, at least about 90%, at least about 95%, or at least about 98%).The gel content of crosslinked oil can measure as follows: make the oil samples that is cross-linked balance some hours in solvent (the every 50mL solvent of oil that such as about 1g to 2g is crosslinked, or the crosslinked oil of 2g is in 50mL solvent).Then from sample, remove desolventizing (part together with any extraction/dissolving of crosslinked oil), and be dried to constant weight.The part of the crosslinked oil be not extracted is gel section.Suitable solvent comprises toluene and chloroform, but the two provides similar result.The gel section of uncrosslinked silane-modified oil can measure as follows: first according to standard method, and uncrosslinked sample is cross-linked.Uncrosslinked oil samples is mixed (oil that such as about 5g is uncrosslinked with about 4 % by weight dibutyl tin laurates) with crosslinking catalyst, under steady temperature and constant relative humidity in confined chamber crosslinked regular time (such as about 25 degrees Celsius and about 100% relative humidity under about 2 days).Crosslinked sample is extracted to measure gel content according to said method.
Before using, silane-modified oil is stored in the impermeable packaging of moisture, to keep anhydrous condition.During use, via any common technology, conventional equipment known in the art can be adopted, compositions is brushed, spraying, dipping or be otherwise administered in substrate, and gained with fully contacting of ambient moisture, compositions is cross-linked.Silane-modified oil also can provide with nonaqueous solvent in the form of a solution, or provides with form of suspension with nonaqueous solvent (such as alcohol such as ethanol, methanol etc.), and described solution or suspension optionally can comprise crosslinking catalyst.Then, solution/suspension can be sprayed in substrate to provide the coating thinner than the coating possible with concentrated silane-modified oil.
Fig. 1 illustrates to have the triglyceride unsaturated oils molecule of 18-carbon aliphatic unsaturated hydrocarbon and the grafting of vinyltrimethoxy silane and cross-linking method and resulting composition (such as the representative component of fatty acid glyceryl ester) as a kind of in three kinds of fatty acid esters.Vinyl groups on silane is opened by graft reaction (such as being caused by peroxide radical initiator, not shown), and by Silane Grafted to hydrocarbon chain.Hydrolyzable silane is at the position previously occupied by the olefinic carbon in crude oil and aliphatic carbon chain covalent bonding.But due to graft reaction, carbon-to-carbon double bond migrates to adjacent carbon-to-carbon pair.Therefore, in silane-modified oil, hydrolyzable silane is at the position replaced by a carbon in the carbon-to-carbon double bond of having moved and carbochain covalent bonding.Be cross-linked by being exposed to water (such as ambient humidity), methoxy group is hydrolyzed subsequently from silicon, thus from formation silanol, described silanol also can and other silanol condensation to form silicone cross-linked key between covalent molecule in cross-linking products.
Silicyl carburetion can compounding in consumer products before, remove the described oil of preparation any reagent used.Described reagent-removal can adopt any known purification methods form known to persons of ordinary skill in the art.Such as, the form that can adopt any volatile reagent of evaporation removing removed by described reagent.Described evaporation can be carried out under vacuo.The silicyl carburetion of gained purification, because being easy to preparation, stablizing and apply compatible with domestic use, therefore may be particularly useful.
antiseptic
Antiseptic can be used in the present invention, to guarantee that product on shelf to invade relative to oxidation, microorganism and the long-time stability of other potential inadvisable chemical conversion.The non-limiting example of antiseptic comprises anti-microbial preservative and antioxidant.
Preferred anti-microbial preservative includes but not limited to: benzalkonium chloride, benzethonium chloride, benzoic acid and salt, benzylalcohol, boric acid and salt, hexadecylpyridinium chloride cetyl trimethyl ammonium bromide, methaform, chlorocresol, CHG or chlorhexidine acetate, cresol, ethanol, hydantoin, imidazolidinyl urea, metacresol, methyl parahydroxybenzoate, nitromersol, o-phenyl phenol, p-Hydroxybenzoate, phenol, phenylmercuric acetate/phenylmercuric nitrate, propyl p-hydroxybenzoate, sodium benzoate, sorbic acid and salt, bata-phenethyl alcohol, thimerosal and their combination.
The preferred antiseptic of one class is antioxidant.Add antioxidant minimize with the oxidizing process occurred after making contact oxygen or under free radical exists or postpone.
Preferred antioxidant antiseptic includes but not limited to a-tocopherol acetas, acetone sulfite., acetylcysteine, ascorbic acid, ascorbyl palmitate, butylated hydroxyanisol (BHA), Yoshinox BHT (BHT), citric acid, cysteine, cysteine hydrochloride, natural d-a-tocopherol, synthesis d-a-tocopherol, dithiothreitol, DTT, thioglycerol, nordihydroguaiaretic acid, propyl gallate, sodium sulfite, sodium sulfoxylate formaldehyde, sodium pyrosulfite, sodium sulfite, sodium thiosulfate, thiourea, tocopherol, and their combination.
optional member
hydroxy-functional organic substance
Hydroxy-functional organic substance can be any organic substance with at least one hydroxyl (-OH) part.Not bound by theory, it is believed that hydroxy-functional organic substance can participate in the crosslinked of silane-modified oil by one or more hydroxylic moieties of hydroxy-functional organic substance by bridging.
The non-limiting example of hydroxy-functional organic substance comprises monosaccharide, disaccharide, oligosaccharide and polysaccharide and functionalized monosaccharide, disaccharide, oligosaccharide and polysaccharide and their derivant.Other non-limiting example comprises cellulose, guar gum, starch, cyclodextrin, hydroxypropyl guar gum, hydroxypropyl cellulose, guar hydroxypropyltrimonium chloride, Polyquaternium-10, dimethiconol, hydroxy-end capped polybutadiene, poly(ethylene oxide), poly(propylene oxide) and poly-(tetramethylene ether) glycol.In specific at one, described hydroxy-functional material comprises more than one oh group, preferred multiple oh group, makes to form bridge between the binding site on multiple silane-modified oil, thus forms gel.Described bridge can be formed the nucleophillic attack of the silyl-group of silicyl carburetion due to the oh group of hydroxy-functional organic substance.
In one aspect, hydroxy-functional organic substance is organosiloxane material such as dimethiconol.Described organosiloxane material can have and is less than about 1,000,000 daltonian molecular weight.Described organosiloxane material can have and is greater than about 1,000,000 daltonian molecular weight.Organosiloxane material can have about 1,000,000 daltonian molecular weight.
In one aspect, described hydroxy-functional organic substance can be polymer.In yet another aspect, described hydroxy-functional organic substance comprises polyvinyl.In yet another aspect, described hydroxy-functional organic substance is hydroxy-end capped polybutadiene.
In one aspect, described hydroxy-functional organic substance is selected from glycol, polyglycols, ether, polyethers, polyalkylene oxide and their derivant and their mixture.In one aspect, described hydroxy-functional organic substance is poly(ethylene oxide), poly(propylene oxide) or their mixture.
In one aspect, described hydroxy-functional organic substance is relative hydrophobic, preferably has about 0.5 to about 14.5 (such as C4-C30), more preferably the cLogP of about 2.9 to about 8.0 (such as C8-C18).Use ChemBioDrawUltra13.0 software, calculate the cLogP of hydroxy-functional organic substance.
hydroxy-functional inorganic particle
Hydroxy-functional inorganic particle is comprise hydroxylic moiety on the surface and any inorganic solid particles in water insoluble or other solvent at them, and described solvent can comprise the carrier of the present composition.The non-limiting example of the functionalized inorganic particle of suitable hydroxyl comprises metal-oxide such as titanium dioxide, aluminium oxide and metallocene, silicon dioxide and zeolite.
As used herein, " silicon dioxide " refers to particulate silica.Those of ordinary skill in the art will recognize, silicon dioxide can take the one in various ways, and described form comprises pyrogenic silica, amorphous silica, precipitated silica, silica gel etc.Those of ordinary skill in the art will recognize, particulate silica can comprise the hydroxylic moiety (i.e. OH group) of multiple surface bond.
In one aspect, hydroxy-functional inorganic particle also can be graininess beneficial agent.Also the non-limiting example that can be the hydroxy-functional inorganic particle of graininess beneficial agent comprises pigment, clay.
In one aspect, hydroxy-functional inorganic particle can have about 3nm to about 500um, preferably about 3nm to about 100um, preferably the particle mean size of about 3nm to about 50um.
surfactant and emulsifying agent
Compositions of the present invention can comprise one or more surfactants or emulsifying agent.Surfactant or emulsifier component are contained in personal care composition of the present invention, to provide clean-up performance.Surfactant can be selected from anion surfactant, zwitterionic surfactant or amphoteric surfactant or their combination.The surface active agent composition be applicable in confectionery composition comprise become known for hair-care, fabric nursing, surface care or other personal nursing and/or home care Cleasing compositions those.
Suitable non-ionic surface active agent includes but not limited to have alkylidene oxygen, in general ethylidene oxygen and aliphatic series, the alcohol of uncle or secondary straight or branched or the phenol rolled into a ball of 6-30 ethyleneoxy group in general.Other suitable non-ionic surface active agent comprises one or dialkyl alkanolamides, alkyl polyglucoside and polyhydroxy fatty acid amide.
The non-limiting example of suitable anion surfactant is alkyl sulfate, alkyl ether sulfate, alkylaryl sulfonates, alkyl succinate, alkyl sulfo succinate, N-Alkanoyl sarcosinates, alkylphosphonic, alkyl ether phosphate, the sodium salt of alkyl ether carboxy acid salt and alpha-alkene sulfonate, ammonium salt and monoethanolamine salt, diethanolamine salt and triethanolamine salt.Alkyl generally comprises 8 to 18 carbon atoms and can be undersaturated.Alkyl ether sulfate, alkyl ether phosphate and alkyl ether carboxy acid salt's per molecule can comprise 1 to 10 ethylidene oxygen or propylidene oxygen unit, and preferably per molecule comprises 2 to 3 ethylene oxy units.The example of anion surfactant comprises sodium lauryl sulfate or ammonium lauryl sulfate and sodium laureth sulfate or Zetesol AP.Suitable anion surfactant used in the present invention generally with by weight of the composition, 5% to 50%, preferably 8% to 30%, more preferably 10% to 25%, even more preferably the scope of 12% to 22% uses.
The non-limiting example of suitable cationic surfactant comprises water solublity or water dispersible or water-insoluble compound, and described compound comprises the amine groups that at least one is preferably quaternary ammonium group, and at least one is preferably the hydrocarbyl group of long chain hydrocarbon group.Alkyl can be hydroxylating and/or oxyalkylated, and can comprise ester group and/or amide groups and/or aryl.Alkyl can be completely saturated or undersaturated.
In one aspect, the content of surfactant can at the weighing scale by described consumer product compositions, and 0.5% to 95%, or 2% to 90%, or in the scope of 3% to 90%.
For the suitable amphion in confectionery composition or amphoteric surfactant comprise become known in hair-care or other personal cleaning compositions those.The concentration of this type of amphoteric surfactant preferably 0.5% to 20%, preferably 1% to 10% scope in.Suitable amphion or the non-limiting example of amphoteric surfactant are described in all authorizes Bolich, and the United States Patent (USP) 5,104,646 and 5,106 of the people such as Jr., in 609.
Be applicable to amphoteric surfactant of the present invention and can comprise alkyl amine oxide, alkyl betaine, alkylamide propyl-betaine, alkyl sulfo betaines, alkyl glycine salt, alkyl carboxyl glycinate, alkyl both sexes propionate, alkylamide propyl hydroxyl sulfo betaine, acyl taurine salt and acyl glutamate, wherein alkyl and carboxyl groups have 8 to 18 carbon atoms.
The non-limiting example being applicable to other anion surfactant in compositions, zwitterionic surfactant, amphoteric surfactant, cationic surfactant, non-ionic surface active agent or optional additional surfactants is described in the EmulsifiersandDetergents of McCutcheon, 1989 annuals, are published by M.C.PublishingCo., and United States Patent (USP) 3,929,678,2,658,072,2,438,091 and 2,528, in 378.
spice and perfume microcapsule
Optional perfume composition can comprise and is selected from following component: the mixture of perfumery oil, perfumery oil, perfume microcapsule, the perfume microcapsule of pressure activated, the perfume microcapsule of moisture-activated are with their mixture.Described perfume microcapsule compositions can comprise 0.05% to 5%; Or the encapsulating material of 0.1% to 1%.Then, described spice core can comprise spice and optional diluent.Described perfume microcapsule also can be particle benefit agent.
The perfume microcapsule of pressure activated generally comprises core-shell configuration, and wherein core material also comprises the mixture of perfumery oil or perfumery oil.Surround described core and can be any applicable polymeric material with the sheathing material forming microcapsule, the material that described polymeric material is impermeable or the material substantially in impermeable core (being generally liquid core) and can contacts with the exterior base of described shell.In one aspect, the material forming microcapsule shell can comprise formaldehyde.Based on formaldehyde resin such as carbamide or urea-formaldehyde resins to spice encapsulating especially attractive, this be due to they be extensively easy to get and cost reasonable.
The perfume microcapsule of moisture-activated comprises the flavor compositions of fragrance carrier and encapsulating, and wherein said fragrance carrier can be selected from cyclodextrin, starch capsules, porous carrier microcapsule and their mixture; And the flavor compositions of wherein said encapsulating can comprise low volatility fragrance component, high volatile volatile fragrance component and their mixture;
(1) front spice;
(2) low Odor Detection Threshold Perfume composition, what wherein said low Odor Detection Threshold Perfume composition can account for the weight of total pure flavor compositions is less than 25%; And
(3) their mixture.
The fragrance carrier that can be used for the adequate moisture activation in disclosed multipurpose fabric-conditioning compositions can comprise cyclodextrin.As used herein, term " cyclodextrin " comprises any one in known cyclodextrin, such as comprise the unsubstituted ring dextrin of six to ten two glucose units, especially beta-schardinger dextrin-, gamma-cyclodextrin, alpha-cyclodextrin and/or their derivant and/or their mixture.The more detailed description of suitable cyclodextrin is provided in USPN.5,714, in 137.Cyclodextrin suitable herein comprises beta-schardinger dextrin-, gamma-cyclodextrin, alpha-cyclodextrin, the beta-schardinger dextrin-of replacement and their mixture.In one aspect, described cyclodextrin can comprise beta-schardinger dextrin-.Perfume molecules to be encapsulated in the cavity of cyclodextrin molecular to form molecular microcapsule, is commonly called cyclodextrin/spice complex.Spice carrying capacity in cyclodextrin/spice complex can account for 3% to 20% by the weighing scale of described cyclodextrin/spice complex, or 5% to 18%, or 7% to 16%.
Described cyclodextrin/spice complex firmly retains the perfume molecules of encapsulating, makes them can prevent spice from spreading and/or perfume loss, thus reduces the odour intensity of multipurpose fabric-conditioning compositions.But in the presence of moisture, described cyclodextrin/spice complex can easily discharge some perfume molecules, thus provides long-lasting perfume benefits.The non-limiting example of preparation method is shown in USPN5, and 552,378 and 5,348, in 667.
particle benefit agent
Particle benefit agent is water insoluble or solid particle in other solvent, and described solvent can comprise the carrier of the present composition, and gives beneficial effect in use.The non-limiting example of particle benefit agent comprises pigment, clay, personal care actives matter such as anti-dandruff active and antiperspirant active and comprises the liquid active substance of encapsulating of perfume microcapsule.
Particle benefit agent can have any size and beneficial effect to be delivered that are suitable for using.In one aspect, described particle benefit agent has the particle mean size being less than about 500 microns.In yet another aspect, described particle benefit agent has the particle mean size being less than about 100 microns.In yet another aspect, described particle benefit agent has the particle mean size being greater than about 3nm.In yet another aspect, described particle benefit agent has the particle mean size of about 1 micron to about 50 microns.
Particle benefit agent can be such as sheet shape, spherical, longilineal or aciculiform or difform, and surface is coated or not coated, porous or atresia, electrically charged or uncharged or part is positively charged or negative charge.Particle benefit agent can the form of powder or predispersion add in compositions.
Pigment comprises coloured or leuco-pigment, coated interference pigment, Optical Bleaching Agent granule and their mixture.The particle mean size of this type of granule can be about 0.1 micron to about 100 microns.These granular materialss can derived from natural and/or synthesis source.
Suitable organic dust particle benefit agent includes but not limited to spherical polymer particles, and it is selected from methylsilsesquioxane resin microsphere, such as Tospearl tM145A (ToshibaSilicone); Poly (methyl methacrylate) micro-sphere, such as, Micropearl tMm100 (Seppic); Crosslinked polydimethylsiloxane spheroidal particle, such as Trefil tMe506C or Trefil tMe505C (DowCorningToraySilicone); Polyamide spheroidal particle, such as PA-12 and Orgasol tM2002DNatC05 (Atochem); Polystyrene microsphere, such as, with title Dynospheres tMthe Dyno granule sold, and with title FloBead tMthe ethylene acrylate copolymer that EA209 (Kobo) sells; Starch ocentyl succinic aluminum, such as DryFlo tM(NationalStarch); Polyethylene microsphere, such as Microthene tMfN510-00 (Equistar), silicone resin, poly methyl silsesquioxane siloxane polymer, the sheet shape powder be made up of L-lauroyl lysine, and their mixture.
Coated interference pigment also can be used for herein.Herein, " coated interference pigment " refers to the thin plate laminate granular with two-layer or more layer controlled thickness.Described layer has the different refractivity producing characteristic reflected colour, described characteristic reflected colour by typical case two kinds, but sometimes multiple luminous reflectance interference effect and produce, described luminous reflectance is from the different layers of plate-like particles.The most Usual examples of coated interference pigment is the TiO with about 50 – 300nm 2, Fe 2o 3, silicon dioxide, stannum oxide and/or Cr 2o 3the Muscovitum of rete.Above-mentioned pigment is generally pearly-lustre.Due to the huge difference of the transparency of granules of pigments and the refractive index of mica sheet and such as coating of titanium dioxide, pearlescent pigment is reflected, refraction and transmitted ray.Coated interference pigment can be commercially available from various supplier, such as Rona (Timiron tMand Dichrona tM), Presperse (Flonac tM), Englehard (Duochrome tM), Kobo (SK-45-R and SK-45-G), BASF (Sicopearls tM) and Eckart (Prestige tM).In one aspect, in coated interference pigment, the average diameter of the most long side surface of independent granule is less than about 75 microns, or is less than about 50 microns.
Other pigment that can be used in the present invention can provide color mainly through the visible ray of selective absorbing specific wavelength, and comprise inorganic pigment, organic pigment, and their combination.The example of this type of available inorganic pigment comprises ferrum oxide, ammonium ferrocyanide ferrum, manganese violet, ultramarine blue and chromium oxide.Organic pigment can comprise monomer coloring agent and the polymeric colorant of natural coloring agent and synthesis.Example is phthalocyanine blue and phthalocyanine green pigment.Color lake is also available, mainly FD & C or D & C color lake and their blend.Also can be solubility or insoluble dyes and other coloring agent of encapsulating.Can be used for the Inorganic white in the present invention or leuco-pigment, such as TiO 2, ZnO or ZrO 2multi-source of can comforming is commercially available, such as TRONOXTiO 2series, SAT-TCR837, rutile TiO2 (U.S.Cosmetics).Also desirably authorize the people such as Ha and be disclosed in United States Patent (USP) 5,997, the charged dispersion of the titanium dioxide in 887.
Clay comprises the silicate and aluminosilicate mineral material with layer structure.The non-limiting example of clay comprises terre verte race clay mineral, such as bentonite, montorillonite clay, beidellite, nontronite, saponite, Strese Hofmann's hectorite., sauconite, humite etc.; Vermiculitum race clay mineral such as Vermiculitum etc.; Kaolin mineral is halloysite, kaolinite, endellite, dicite etc. such as; Phyllosilicate is Talcum, pyrophyllite, Muscovitum, emerylite, white mica, phlogopite, four silicon Muscovitums, taincolite etc. such as; Serpentine race mineral such as antigorite etc.; Chlorite race mineral such as chlorite, cookeite, nepouite etc.These layered inorganic compounds can be natural product or synthetic product.These can used aloned or use with the combining form of two or more.
Anti-dandruff active reduces the active substance that the dandruff is formed when being and being deposited on scalp.Described anti-dandruff active substance can be selected from: pyrithione; Azole, such as ketoconazole, econazole and Xin Kang azoles; Selenium sulfide; Granule sulfur; Keratolytic agent is salicylic acid such as; And their mixture.Pyrithione can for suitable anti-dandruff active granule.In one aspect, described anti-dandruff active matter can be pyrithione salt, and in particle form.In one aspect, the concentration of Pyridinethione anti-dandruff granule about 0.01 % by weight to about 5 % by weight, or about 0.1 % by weight to about 3 % by weight, or in the scope of about 0.1 % by weight to about 2 % by weight.In one aspect, pyrithione is those that formed by heavy metal such as zinc, stannum, cadmium, magnesium, aluminum and zirconium (being generally zinc), be generally the zinc salt (being called " Zinc Pyrithione " or " ZPT ") of pyrithione, be generally the pyrithione salt of flaky particle form.In one aspect, the pyrithione salt of flaky particle form has about 20 microns at the most, or about 5 microns at the most, or the particle mean size of about 2.5 microns at the most.The salt formed by other cation such as sodium also can be suitable.
Antiperspirant active comprises any compound, compositions or other material with antiperspirant active.More specifically, antiperspirant active can comprise astringent metallic salts, especially the inorganic salt of aluminum, zirconium and zinc and organic salt and their mixture.Even more specifically, antiperspirant active can comprise containing aluminum and/or the salt or material, such as aluminum halide, aluminium chlorohydrate, hydroxyhalides, zirconyl oxyhalides oxygen zirconium, hydroxyhalide oxygen zirconium and their mixture that contain zirconium.
other
According to form (the such as shampoo that consumer products use, liquid soap, bath shampoo, laundry detergent compositions, fabric softener), these compositionss also can comprise and are selected from following composition: the fatty alcohol with 8 to 22 carbon atoms, the glycol ester of opacifier or pearling agent such as fatty acid (such as, diglycol stearate), viscosity modifier, buffer agent or pH regulator chemical substance, comprise water-soluble polymer that is crosslinked and non-cross-linked polymer, suds booster, dyestuff, coloring agent or pigment, herb extract, hydrotropic agent, enzyme, bleach, fabric conditioner, fluorescent whitening agent, stabilizing agent, dispersant, soil releasing agent, anti-wrinkle agent, chelating agen, anticorrosive, and their mixture.
example
Be limiting examples of the present invention below.Described example only provides for purpose of explanation should not be understood to restriction of the present invention, because their modification many are possible and do not deviate from the spirit and scope of the invention, this will be recognized by those of ordinary skill in the art.
In instances, except as otherwise noted, all concentration is all listed with percentage by weight, and eliminates minor materials, as diluent, filler etc.Therefore, listed preparation comprises listed component and any minor materials relevant with this component.It is evident that for those of ordinary skills, the selection of these microcomponents changes according to selected with the Physical and chemical characteristics of the concrete composition preparing invention as described herein.
shi Li – materials synthesis
example 1-silylanizing, option one
Mixing soya beans oil (290g), vinyltrimethoxy silane (246g) and 2 in airtight flask, 5-two (tert-butyl peroxy base)-2,5-dimethylhexane peroxide (LUPEROX101) initiator (2.90g).Use nitrogen seals, and is pumped into by mixture in 2LParr hydrogenator and (derives from ParrInstrumentCompany, Moline, Ill., USA), and before introducing reactant mixture, described hydrogenator nitrogen purges 5 minutes to guarantee water-less environment.The temperature of reactor is established to 240 degrees Celsius, and stirring is remained on 200rpm, with mixed reactant even heat is dispersed in system.Collect the silylanizing soybean oil product after 10 little the reaction times.
example 2-silylanizing, option 2
In the 2LParr4520 high-pressure reactor being equipped with overhead type stirring motor and electric thermo-couple temperature to control, add soybean oil (290g), vinyltrimethoxy silane (246g) and Luperox101 (2,5-pair-(tert-butyl peroxy base)-2,5-dimethylhexane diperoxy compound, 2.90g) initiator.Reaction is heated 24h at 225 DEG C, is then cooled to RT.
General VTMOS and the soybean oil using 1:1,2:1 and 3:1 mol ratio, synthesis silylanizing soybean oil.These obtain the average silylanizing degree of the oily oil of the silyl-group every mole of 0.7,1.5 and 2.4 mole respectively.
The silylanizing Abyssinia oil that the VTMOS of general use 1:1 and 2:1 ratio and Abyssinia's oil synthesize, the average silylanizing degree of the oil that the silyl-group every mole of acquisition 0.8 and 1.3 mole is oily respectively.
The silylanizing high gas oil ratio soybean oil that the VTMOS of general use 1:1 and 2:1 ratio and high gas oil ratio soybean oil synthesize, the average silylanizing degree of the oil that the silyl-group every mole of acquisition 0.8 and 1.7 mole is oily respectively.
The silylanizing low erucic acid rapeseed oil that the VTMOS of general use 1:1 and 2:1 ratio and low erucic acid rapeseed oil synthesize, the average silylanizing degree of the oil that the silyl-group every mole of acquisition 0.9 and 1.4 mole is oily respectively.
After the such as purification described in example 3, by thermogravimetric analysis, all silicyl carburetion are carried out to the evaluation of silicyl content.
example 3– removes excessive reagent from silylation reactive
Heat up in a steamer 3-5 hour by rough product to be positioned in rotary evaporator and to carry at vacuum (0.1-10mmHg) and about 80 DEG C, remove excessive sillylation reagent.
example 4
Dibutyl tin laurate (0.1g) is joined in the sample (5g) of example 1.Gained sample directly can use or under humidity exists, (ambient humidity is to 100%RH) can be heated to the temperature of 100 DEG C at the most, and then uses further.(" RH "=relative humidity)
example 5- semen sojae atricolor-Si-granule
The silylanizing Semen sojae atricolor (5g) deriving from example 1 is mixed with the granule of size within the scope of 0.003-500um of 0.10,0.20 and 0.55g.Gained sample directly can use or under humidity exists, (ambient humidity is to 100%RH) can be heated to the temperature of 100 DEG C at the most.
Use and suitable have the functionalized hydroxylization granule of similar size and the said method of this example, those of ordinary skill in the art can evaluate the soybean particle of following modification:
example 6- semen sojae atricolor-Si-polymer
To in the silylanizing Semen sojae atricolor (5g) deriving from example 1, add dimethiconol (5g).Gained mixture directly can use or under humidity exists, (ambient humidity is to 100%RH) can be heated to the temperature of 100 DEG C at the most.Subsequently can corresponding preparation products therefrom, as in hereafter consumer products example.
Use the method for suitable functionalized polymeric and example 5, multiple soy-derived granule interpenetrating networks can be obtained, comprising:
-Semen sojae atricolor-Si-PEO-Semen sojae atricolor-Si-PPO-Semen sojae atricolor-Si-PTMG
The polybutadiene that-Semen sojae atricolor-Si-is hydroxy-end capped
example 7
By the silylanizing Semen sojae atricolor (5g) deriving from example 1 and dimethiconol (5g) and 0.10,0.20 or the hydroxyiated functional granule of granularity within the scope of 0.003-500um of 0.55g mix.Gained sample directly can use or under humidity exists, (ambient humidity is to 100%RH) can be heated to the temperature of 100 DEG C at the most.Corresponding preparation products therefrom subsequently, in such as this paper consumer products example.
shi Li – emulsion
All compositionss of evaluation proper property according to Examples below 8-10, can be mixed with water-based emulsion.Prepare silicyl carburetion as mentioned above and use standard emulsification program to use sodium lauryl sulphate emulsifying (being generally 30% oil and 0.75%SDS).The silicyl carburetion of emulsifying and optional hydroxylating organic substance or hydroxylating inorganic particle is used to prepare compositions.
By the former state that obtained emulsion receives, use hydroxy-end capped PDMS (dimethiconol).Two samples can business preparation (DC1872 derives from the 68000cSt dimethiconol of DowCorning, or derives from the MEM1788 of Xiameter, 2000000cSt dimethiconol).By the emulsion polymerization of silanol stopped dimethylsiloxane oligomer and DBSA, prepare intermediate molecule amount (1000000cSt dimethiconol).
Resulting materials (such as silicyl carburetion, silicyl carburetion+catalyst, silicyl carburetion+silicon dioxide, silicyl carburetion+dimethiconol or silicyl carburetion+silicon dioxide+dimethiconol) in example 1-7 also can be made with the simple emulsion with certain particle size distribution of at least 0.1% test material concentration (wt/wt) at deionized water, they at room temperature stable at least 48 hours.It will be apparent to one skilled in the art that and multiple different surfactant or solvent can be used to prepare this type of emulsion, this depends on the feature of often kind of concrete material.Can be used successfully to and form the surfactant of this type of suspension and the example of solvent and comprise: ethanol, hTL8-MS or 2HT-75, glyceryl monooleate, Tergitol tM15-S, Tergitol tMtMN, TergitolNP, Tween, Span, straight-chain alkyl sulfate such as sodium lauryl sulphate or Brij and their mixture.It will be apparent to one skilled in the art that by using multiple high-shear mixer, by component being mixed, this type of suspension can be obtained.The example of suitable homogenizer comprises ultra-Turrax or Silverson.
example 8
The silicyl carburetion deriving from example 1 also can be made with the simple emulsion with certain particle size distribution of at least 0.1% test material concentration (wt/wt) in deionized water, and they at room temperature stable at least 48 hours.Solvent as above, surfactant and treatment facility can be used to prepare described emulsion.
example 9
With the ratio of 1:0.01 to 1:10, the fused silica of the silicyl carburetion with the granularity had within the scope of 0.003-5um that derive from the emulsifying of example 8 or other hydroxy-functional granule with similar granularity are mixed.
example 10
Mix with the fused silica (or other hydroxy-functional granule) of the ratio of 1:0.01 to 1:10 by the silicyl carburetion with the granularity had within the scope of 0.003-5um that derive from the emulsifying of example 8, and mix with hydroxy-functionalized polymer's such as dimethiconol of emulsifying.
shi Li – proper property
Show that the example of present composition proper property is shown in table 1-5.Can according to example 3 at compounding front purification for what show silane-modified oil in 1-5 example.
The emulsion compositions process as shown in Table of fabric substrate use is with common acquisition 1mg, 3mg or 10mg oil (described oil is silicyl carburetion, OH-functionalized polymeric or silicyl carburetion+OH-functionalized polymeric) every gram of fabric.By all substrate dryings processed before test, and can at least 24 hours be balanced.Fabric in testing for secant modulus is 100% mercerising combing sateen fabric warp, and about 155 grams/m, #479 type, purchased from TestFabrics (WestPittston, PA).Fabric in measuring for Wicking Time is without brightening agent stripes purchased from the CW120 type of EMC.Be described in compositions in table 3 before the use, use the pH of the further pH regulator to 10.5 of 1MNaOH solution.
Be sending out bunch of the no special quality of toffee for the hair substrate in testing, purchased from InternationalHairImporters & Products (Glendale, NY).Emulsion compositions process shown in hair substrate table, obtain 10mg oil (described oil is silicyl carburetion, OH-functionalized polymeric or silicyl carburetion+OH-functionalized polymeric) every gram of substrate altogether, and it is dry under 70F/50%RH (relative humidity), then after 24 hours, in 50C baking oven dry 15 minutes.
wicking Time
Wicking Time is that compositions gives measuring of repellents ability to the fabric processed.Not bound by theory, it is believed that the Wicking Time of increase is associated with repellents relative to the fabric of the increase of dyeing.Following mensuration fabric wicking time response.
Test in the room of 20 to 25 DEG C of air themperatures and 45-55% relative humidity or indoor.Before collecting measured value, all fabrics used and paper products in test are balanced at least 24 hours under the temperature and humidity condition of test site.The test fabric processed is cut into 10 squares, is eachly of a size of about 1.25 " × 1 ".In smooth level and on the surface of smooth impermeable, 10 independent squares are placed on the surface of a slice kitchen towels (such as Bounty).It is not the surface directly contacting placement during prepared by fabric with treatment compositions with the surface upward of wipe contacts.Visual confirmation before treatment fabric flat and with napkin uniform contact.
Then the fabric of smooth placement is carried out to the test of Wicking Time measurement.Use distilled water as test liquid.Automatic list or multichannel pipet (such as Rainin, Gilson, Eppendorf) is used to be delivered on fabric face by 300 μ L test liquids of certain drop size.Use stopwatch or intervalometer, from the moment of drop contact fabric face, with minute and clock second.When integral drip test liquid absorbs in fabric, stop intervalometer.Via visualization, time point when determining in drop moistening to fabric.The elapsed time section that intervalometer illustrates is the Wicking Time measured.If do not observe drop moistening yet, then stop test after 60 minutes, and be >60 minute by the Wicking Time surveying record in this situation.If find liquid moistening immediately when drop and surface contact, then the Wicking Time characteristic of this fabric is designated as 0.Totally 10 dropping liquids measuring difference place in test fabric drip, and these 10 times measurements are averaged, to provide the Wicking Time value of report.
secant modulus reduces
It is that compositions gives measuring of the ability of flexibility to the fabric processed that secant modulus reduces (RSM).Not bound by theory, it is believed that lower secant modulus is associated with the fabric of higher flexibility, described fabric is thought more soft by consumer.Notice, RSM is reported to and reduces relative to the secant modulus of tester, thus higher report value is associated with lower secant modulus and excellent flexibility result.
Use has for controlling test speed and other test parameter, and carries out RSM measurement for the business tensile tester of the computer interface collecting, calculate and report data.The Instron5544 test system running Bluehill software kit is used to carry out RSM test.Controlling to test to 20 to 25 DEG C of air themperatures and control to the room of 50% relative humidity (RH) or indoor.Before collecting measured value, all fabrics used in test are balanced at least 16 hours under the temperature and humidity condition of test site.
Test period, selects load sensor, makes tension response from tested sample by between 10% and 90% of load sensor capacity or in load range used.Typically, the load sensor of 500N is used.Select holder, make them enough wide with adaptive fabric sample, and the fabric slippage of test period is minimized.Usually, employing is established to 60psi pressure and is furnished with the pneumatic type holder of 25.4mm square reticulate patterned surface.According to the guidance of manufacturer, by instrument calibration.By holder in the face of neat, and gauge length is established to 25.4mm (or 1 inch).Fabric sample is loaded in pneumatic type holder, makes warp-wise be parallel to collet movement direction.Enough tension force is applied to fabric strip, observable lax to eliminate, but make load sensor reading be no more than 0.5N.Following employing multi-step scheme test sample book:
(step 1) reaches the strain of 10% with the constant rate of speed of 50mm/min, is then back to the strain of 0% with the constant rate of speed of 50mm/min.This is the first hysteresis cycle.
(step 2) keeps 15 seconds and clamps sample again under 0% strain, any observable lax to eliminate, and keeps 25.4mm gauge length, and does not make load sensor reading exceed 0.5N.
(step 3) reaches the strain of 10% with the constant rate of speed of 50mm/min, is then back to the strain of 0% with the constant rate of speed of 50mm/min.This is the second hysteresis cycle.
(step 4) keeps 15 seconds and clamped sample again under 0% strain, any observable lax to eliminate, and keeps 25.4mm gauge length, and does not make load sensor reading exceed 0.5N.
(step 5) reaches the strain of 10% with the constant rate of speed of 50mm/min, is then back to the strain of 0% with the constant rate of speed of 50mm/min.This is the 3rd hysteresis cycle.
(step 6) keeps 15 seconds and clamped sample again under 0% strain, any observable lax to eliminate, and keeps 25.4mm gauge length, and does not make load sensor reading exceed 0.5N.
(step 7) reaches the strain of 10% with the constant rate of speed of 50mm/min, is then back to the strain of 0% with the constant rate of speed of 50mm/min.This is the 4th hysteresis cycle.
Use initial sample dimension, the gained tension force displacement data deriving from the 4th hysteresis cycle (step 7) is transformed into load-deformation curve, draws secant modulus used herein thus.Initial sample dimension be 25.4mm wide × 25.4mm length × 0.41mm is thick.4th circulation secant modulus of 10% strain place is defined as the slope at the 4th the hysteresis cycle 0% and 10% strain place straight line crossing with load-deformation curve.For each fabric treating, measure minimum three fabric samples, and gained the 4th circulation secant modulus is averaged, to obtain the average 4th circulation secant modulus at 10% place.By calculating the percentage ratio making 10% strain place the 4th circulation secant modulus decline with the given compositions compared with water-treated control fabric sample, compare the proper property of the present composition.
The report value of average RSM percentage ratio is calculated as:
water is taken in and is reduced
Water absorption is reduced to compositions and gives measuring of the ability of whole day control to hair.Not bound by theory, it is believed that the water of hair is taken in and cause hair style to be destroyed and " curling ", make consumer feel that water is taken in because the whole day improved controls and reduce.Via the Dynamic Vapor Sorption (DVS) at 25 DEG C, determination techniques beneficial effect.
In DVS experiment, first make hair expose 30 hours under 0%RH, then humidity is risen to 90%RH, and constant maintenance 16 hours under 90%RH.Data be reported to and take in minimizing % relative to the water of water tester, wherein water is taken in and is provided by hair gross mass increase %, is rendered as the water under the 90%RH compared with 0%RH baseline.
table 1--fabric comprises the selected soybean oil based silicyl having He do not have silicon dioxide the compositions of carburetion and selected dimethiconol
1with Nalco1115 purchased from Nalco (Naperville, IL).Percentage by weight is reported with active silica %.
2dowCorning (Midland, MI) is derived from trade name DC1872.Percentage by weight is listed with active polydimethylsiloxane alcohol %.
3by purchased from Gelest (Morrisville, PA) silanol stopped dimethylsiloxane oligomer is listed with active polydimethylsiloxane alcohol % with percentage by weight obtained purchased from the emulsion polymerisation of the DBSA of SigmaAldrich (St.Louis, MO).
4xiameter (subsidiary of DowCorning (Midland, MI)) is derived from trade name MEM-1788.Percentage by weight is listed with active polydimethylsiloxane alcohol %.
5sodium lauryl sulphate, purchased from SigmaAldrich (St.Louis, MO).
compositions on table 2--hair
1dowCorning (Midland, MI) is derived from trade name DC1872.Percentage by weight is listed with active polydimethylsiloxane alcohol %.
2xiameter (subsidiary of DowCorning (Midland, MI)) is derived from trade name MEM-1788.Percentage by weight is listed with active polydimethylsiloxane alcohol %.
3sodium lauryl sulphate, purchased from SigmaAldrich (St.Louis, MO).
table 3--fabric comprises the selected triglyceride monosilane having He do not have silicon dioxide the compositions of base carburetion
1with Nalco1115 purchased from Nalco (Naperville, IL).Percentage by weight is reported with active silica %.
2xiameter (subsidiary of DowCorning (Midland, MI)) is derived from trade name MEM-1788.Percentage by weight is listed with active polydimethylsiloxane alcohol %.
3sodium lauryl sulphate, purchased from SigmaAldrich (St.Louis, MO).
the compositions comprising selected particle benefit agent on table 4--fabric
1with SytonHT-50 purchased from SigmaAldrich (St.Louis, MO)
2with AFDC200 purchased from KoboProducts, Inc. (SouthPlainfield, NJ)
3purchased from EMDChemicals (Philadelphia, PA)
4purchased from BASF (Iselin, NJ)
5purchased from WackerSilicones.Percentage by weight is listed with active polydimethylsiloxane alcohol %.
6the used emulsifying agent comprising Tween80 and Span80, purchased from SigmaAldrich (St.Louis, MO)
the compositions comprising selected hydroxy-functional organic substance on table 5--fabric
1purchased from SigmaAldrich (St.Louis, MO)
2with NHanceCG-17 purchased from AshlandInc. (Wilmington, DE)
3the used emulsifying agent comprising Tween80 and Span80, purchased from SigmaAldrich (St.Louis, MO)
shi Li – consumer products
example 11
Shampoo-prepare shampoo Compositions by following component by conventional method.
1 aT-1, the copolymer of acrylamide (AM) and TRIQUAT, MW=1,000,000; CD=1.6meq./g; 10% active substance; Supplier Rhodia
2 c500, MW – 500,000, CD=0.7, supplier Rhodia
3 100S, 31.5% active substance, supplier Rhodia
4sodium laureth sulfate, 28% active substance, supplier: P & G
5sodium lauryl sulfate, 29% active substance, supplier: P & G
6 betanin F-B, 30% active substance, supplier: GoldschmidtChemicals
7monamidCMA, 85% active substance, supplier GoldschmidtChemical
8diglycol stearate, EGDS is pure, supplier GoldschmidtChemical
9sodium Chloride USP (food stage), supplier Morton; Note, salt is adjustable composition, can add higher or lower content to obtain target viscosities.
example 12
Conditioner Shi Li – prepares conditioner composition by conventional method by following component.
Example compositions A B
Composition
Water Appropriate to 100% Appropriate to 100%
The silicyl carburetion of example 1-10, in the active substance % by weight of oil 1 1.0 --
The silicyl carburetion of example 1-10, in the active substance % by weight of oil 2 -- 1.0
Cyclopentasiloxane 3 -- 0.61
INCROQUAT TMC-80 ECONOL TM22 4 2.25 2.25
Isopropyl alcohol 0.60 0.60
Spermol 5 1.86 1.86
Stearyl alcohol 6 4.64 4.64
Disodiumedetate 0.13 0.13
NaOH 0.01 0.01
Benzylalcohol 0.40 0.40
Methylchloroisothiazandnone/Methylisothiazolinone 7 0.0005 0.0005
Pantothenylol 8 0.10 0.10
Panthenyl ethyl ether 9 0.05 0.05
Aromatic 0.35 0.35
1the silicyl carburetion of example 1-10, in the active substance % by weight (also can use their mixture) of oil
2the silicyl carburetion of example 1-10, in the active substance % by weight (also can use their mixture) of oil
3cyclopentasiloxane: SF1202, purchased from MomentivePerformanceChemicals
4iNCROQUAT TMC-80 ECONOL TM22/isopropyl alcohol: GenaminTMKMP, purchased from Clariant
5spermol: KonolTM series, purchased from ShinNihonRika
6stearyl alcohol: KonolTM series, purchased from ShinNihonRika
7methylchloroisothiazandnone/Methylisothiazolinone: KathonTMCG, purchased from Rohm & Haas
8pantothenylol: purchased from Roche
9panthenyl ethyl ether: purchased from Roche
example 13
Bath shampoo example-following preparation comprises the bath shampoo of the silicyl carburetion of example 1-10.Water is added in mixer, add sodium chloride, water-soluble cationic polymer, lauroyl amido CAB, tridecyl sulfate, the tridecyl alcohol of ethoxylation, antiseptic, sequestering agent and association polymer afterwards with continuous stirring until evenly.With oxidant by pH regulator to pH=5.7 ± 0.2.Pass through SpeedMixer tM, with the speed of 1,000rpm through 60 seconds, the silicyl carburetion of example 1-10 is added surfactant mutually in.
Composition
Distilled water In right amount
Sodium trideceth sulfate 12.6
Lauroyl amido CAB 7.67
Sodium chloride 4.75
Iconol TDA3-ethoxylated tridecyl base alcohol 1.40
N-Hance CG17 cation guar gum 0.42
Antiseptic 1 0.28
Antiseptic 2 0.037
Association polymer 0.15
Sequestering agent 0.15
Oxidant (50% solution) 0.07
The silicyl carburetion of example 1-10, in the active substance % by weight of oil 1-50
example 14
moisture retention water bag oily skin emulsion/cream
1purchased from Koboproducts
2palmitoyl-lys-thr, purchased from Sederma
3the Muscovitum violet coated interference pigment of titanium dioxide-coated, purchased from Eckart
4the red coated interference pigment of Muscovitum of silicon dioxide and titanium dioxide-coated, purchased from Rona
In appropriate vessel, water-phase component is mixed and is heated to 75 DEG C.In independent appropriate vessel, oil-phase component is mixed and is heated to 75 DEG C.Then, oil phase is joined aqueous phase, and grind gained emulsion (such as using TekmarT-25).Then, thickening agent is added emulsion, and while stirring, emulsion is cooled to 45 DEG C.Residual components is added at 45 DEG C.Under agitation product is cooled to 30 DEG C, and is poured in suitable container.
example 15
Water-covered siloxane elite/the emulsion of moisturizing:
1gLW75CAP-MP, derives from a 75% aqueous titanium dioxide prose style free from parallelism of Kobo
2purchased from the palmitoyl-lys-thr of Sederma
5derive from the titanium dioxide of Engelhard and the green coated interference pigment of Muscovitum of stannum oxide coating
6derive from the red coated interference pigment of Muscovitum of the titanium dioxide-coated of Eckart
In suitable container, water-phase component is merged and mixes until evenly.In independently suitable vessel, siloxanes/oil-phase component is merged and mixes until evenly.Independently, by being mixed by premix ingredients in suitable container, while stirring, be heated to about 70 DEG C, and be cooled to room temperature to prepare two palmityl hydroxyproline premix and/or undecylenoyl phenylalanine pre-composition while stirring.By half thickening agent, then siloxanes/oil phase is added in aqueous phase, and grind the emulsion (such as using TekmarT-25) of gained.By remaining thickening agent, two palmityl hydroxyproline premix and/or undecylenoyl phenylalanine pre-composition while stirring, then residual components is added in emulsion.Once compositions is even, just product is poured in suitable container.
example 16
water-covered siloxane mousse
1gLW75CAP-MP, derives from a 75% aqueous titanium dioxide prose style free from parallelism of Kobo
2purchased from the palmitoyl-lys-thr of Sederma
5derive from the titanium dioxide of Engelhard and the green coated interference pigment of Muscovitum of stannum oxide coating
6derive from the red coated interference pigment of Muscovitum of the titanium dioxide-coated of Eckart
In suitable container, water-phase component is merged and mixes until evenly.In independently suitable vessel, siloxanes/oil-phase component is merged and mixes until evenly.Independently, by being mixed by premix ingredients in suitable container, while stirring, be heated to about 70 DEG C, and be cooled to room temperature to prepare undecylenoyl phenylalanine and/or two palmityl hydroxyproline premix while stirring.By half thickening agent, then siloxanes/oil phase is added in aqueous phase, and grind the emulsion (such as using TekmarT-25) of gained.By remaining thickening agent, undecylenoyl phenylalanine and/or two palmityl hydroxyproline premix while stirring, then residual components is added in emulsion.Once compositions is even, just product is poured in suitable container.Product and propellant are added in aerosol container.Described aerosol container is sealed.
example 17
Antiperspirant ointment/cream is prepared by following component by conventional method.
Example A B C D
Component
The glycinate (solid) of alkali formula aluminum chloride zirconium 25.25 25.25 25.25 25.25
Polydimethylsiloxane (10cs) 5.00 5.00 5.00 5.00
Complete all hydrogenated high erucic acid rape seed oil (HEAR oil) 5.00 5.00 5.00 5.00
Agmatine 2.50 2.50 2.50 2.50
C18-36 acid triglyceride Syncrowax HGLC 1.25 1.25 1.25 1.25
Spice 0.75 0.75 0.75 0.75
Calcium pantothenate (solid) 0.50 0 3.50 0
BHT 0.50 0.50 0.50 0.50
Tocopherol acetas 0.50 0 0.50 0
The silicyl carburetion of example 1-7 In right amount In right amount In right amount In right amount
Amount to 100.00 100.00 100.00 100.00
example 18
Following preparation comprises the muffin of the present invention of the silicyl carburetion of example 1-7:
In the appropriate vessel being equipped with heating source, by pigment, TiO 2the silicyl carburetion of (micronization through siloxane treated), hydrophobicity Talcum, example 1-7, Cyclomethicone (DC245) and dimethicone copolyol (DC5225C) mixing, until evenly, then use SilversonL4RT agitator with 9000rpms grinding until the granularity expected.Then, propyl p-hydroxybenzoate and glycerol are added in said mixture and also mix until evenly.Then mixture is heated to the temperature between 85-90 DEG C, now under agitation adds ceresine (being molten in mixture) until mixture is even.Then, mixture to be poured in mould and to make it be cooled to room temperature.Once cooling, just mixture is mixed in suitable packaging.
Muffin is applied to face to provide the sensation of color, moisturizing and improvement.
example 19
hand dishwashing composition example *
*carbon number in alkyl chain is between 12 and 13; And x is between 0.5 and 2.
Ethylan the non-ionic surface active agent based on synthesis primary alconol, commercially available from AkzoNobel.
tO7 is by saturated iso-C 13the non-ionic surface active agent that alcohol is made.
Solvent is ethanol.
Amine oxide is cocoyl dimethyl amine.
1glutamic acid-N, N-oxalic acid
2diethylenetriamine pentamethyl phosphonic acids
*example can comprise other optional composition, such as dyestuff, opacifier, spice, antiseptic, hydrotropic agent, processing aid, salt, stabilizing agent etc.
example 20
other suitable Cleasing compositions *
*carbon number in alkyl chain is between 12 and 13; And x is between 0.5 and 2.
Ethylan the non-ionic surface active agent based on synthesis primary alconol, commercially available from AkzoNobel.
tO7 is by saturated iso-C 13the non-ionic surface active agent that alcohol is made.
Solvent is ethanol.
Amine oxide is cocoyl dimethyl amine.
1glutamic acid-N, N-oxalic acid
2diethylenetriamine pentamethyl phosphonic acids
3diethylene triamine pentacetic acid (DTPA)
4mDGA
*example can comprise other optional composition, such as dyestuff, opacifier, spice, antiseptic, hydrotropic agent, processing aid, salt, stabilizing agent etc.
example 21
The Fabrid care composition added by rinsing and softening/Fabric Style instrument test rinsing is not bound by theory, and it is believed that fabric extracts can be that the technology of fabric softness is measured.In this test, the compositions of use-case 21 in rinse cycle, makes knop cloth process in automatic miniature washing machine.
It is the white looped pile cloth towel manufactured by StandardTextile for the fabric in miniature washer.Brand name is EuroTouch, and is made up of 100% cotton.By fabric to hemisect, to reach the weight of 50-60 gram, and use standard method destarch.Four and half bar towels are mixed with additional 100% cotton ballast processed, to reach total fabric weight of 250-300 gram of every miniature washer.First in 6GPG (the heavy per gallon of the GPG=hardness grain) water of 2 gallons, with the TideFree & Gentle laundry detergent compositions laundering of textile fabrics of 5.84g dosage.During rinse cycle, add the fabric treating thing that 2.4g rinsing is added.Rinsing and after revolving and getting rid of loop ends, by fabric rotary drying.Prepare one group of benchmark fabric, in the 6GPG of 2 gallons (the heavy per gallon of GPG=hardness grain) water, wash with the TideFree & Gentle laundry detergent compositions of 5.84g dosage, wherein do not add the fabric treating thing that rinsing is added.Rinsing and after revolving and getting rid of loop ends, by fabric rotary drying.With regard to each process comprising benchmark fabric, complete totally three washing-rinsing-dry cycle.
Use the Fabric Style instrument fabric evaluating system manufactured by NuCybertek, Inc (Davis, California), measure and extract energy.The fabric processed is cut into the disk of 11cm diameter, and before the assay, in steady temperature (CT) room, balances 24 hours.CT Room temperature is 20-25 degree Celsius, and relative humidity is 50%.Fabric disk is placed between 2 rings.Apical ring is weighed, and can change based on fabric type.Fabric is pushed through the hole (perpendicular to fabric face) on ring by little probe.Instrument record take time as the power (for voltage) be pushed through by fabric needed for ring of function.Between each fabric is measured, with the alcohol cleaning piece with 70% isopropyl alcohol and 30% deionized water, clean bottom counterweight, inside ring and place the pedestal of ring.Alcohol cleaning piece is purchased from VWRInternational.All initial datas export in MicrosoftExcel.There are in each derived curve 108 data points, but only use first 85.Summation from 1 to 85 integration, and is reported to " the extracting energy " without unit by each curve.For each test processes thing, evaluate minimum 8 fabric disks (in four parts of looped pile clothes, every portion provides two disks), and calculation sample standard deviation.By deducting the average extraction energy of the fabric sample with test group process in following table from the average extraction energy of tester sample, obtain " extract and can reduce " (EER).Not bound by theory, higher EER represents the softening performance of Geng Gao.
By by under be shown as the Fabrid care composition point mixing obtained rinsing and add:
1(tallowoyl base ethyl) – N, N alkyl dimethyl ammonium chloride, purchased from EvonikCorporation, Hopewell, VA for N, N bis-.
2cationic polyacrylamide polymer, the copolymer of such as acrylamide/[2-(acrylamido) ethyl] trimethyl ammonium chloride (quaternised dimethyl amino ethyl acrylate), can trade name Sedipur544 from BASF, AG, Ludwigshafen are commercially available.
3before joining compositions, silylanizing Semen sojae atricolor is emulsified into 20 % by weight fat liquor with BrijO2 and BrijO10.The percentage by weight of listing in table is active silyl soybean oil.
4purchased from AppletonPaper (Appleton, WI)
5xiameter (subsidiary of DowCorning, Midland, MI) is derived from trade name MEM-1788 as emulsion.Percentage by weight is listed as active polydimethylsiloxane alcohol %.
6with Nalco1115 purchased from Nalco, Naperville, IL.Percentage by weight is reported as active silica %.
7with trade name the DDAC of 2280 or with trade name hTL8-MS is purchased from hydrogenated tallow alkyl (2-ethylhexyl) the dimethyl methyl ammonium sulfate of AkzoNobel.
*other optional reagent/component comprise foam inhibitor, structural agent such as based on castor oil hydrogenated (preferred castor oil hydrogenated, anion pre-composition) those, dyestuff, solvent, spice and/or aesthetic property reinforcing agent.
example 22
By the fabric treating thing that washing flexibility/friction testing rinsing is added
Not bound by theory, it is believed that fabric abrasive is that the technology of fabric softness is measured.In this test, the compositions of use-case 22 in rinse cycle, makes knop cloth process in automatic miniature washing machine.
It is the white looped pile cloth towel manufactured by StandardTextile for the fabric in miniature washer.Brand is EuroTouch, and is made up of 100% cotton.By fabric to hemisect, to reach the weight of 50-60 gram, and use standard method destarch.Four and half bar towels are mixed with additional 100% cotton ballast processed, to reach total fabric weight of 250-300 gram of every miniature washer.First in 6GPG (the heavy per gallon of the GPG=hardness grain) water of 2 gallons, with the TideFree & Gentle laundry detergent compositions laundering of textile fabrics of 5.84g dosage.During rinse cycle, the fabric treating thing that the rinsing adding 4.73g is added.Rinsing and after revolving and getting rid of loop ends, by fabric rotary drying.Prepare one group of benchmark fabric, in the 6GPG of 2 gallons (the heavy per gallon of GPG=hardness grain) water, wash with the TideFree & Gentle laundry detergent compositions of 5.84g dosage, wherein do not add the fabric treating thing that rinsing is added.Rinsing and after revolving and getting rid of loop ends, by fabric rotary drying.With regard to each process comprising benchmark fabric, complete totally three washing-rinsing-dry cycle.
At the end of fabric drying, all weaving cotton cloth is made to balance minimum 8 hours under 20-25 degree Celsius and 50% relative humidity.In 2 days of process, measure and processed and equilibrated fabric.During balance, the fabric processed to be kept flat and stacking, be highly no more than 10 fabrics.Degree of friction is measured and is all carried out under the environmental condition identical with condition used during conditioning/equilibrium step.
The Thwing-AlbertFP2250 with 2 kilogram load sensors rubs/peels off tester for measuring fabric to fabric abrasive.(ThwingAlbertInstrumentCompany(WestBerlin,NJ))。Sliding part has the pinching sliding part (ThwingAlbert, model 00225-218) that 6.4 are multiplied by 6.4cm occupied area and 200 gram weight.Distance between load sensor and sliding part is set to 10.2cm.By clamper arm apart from the altitude mixture control of sample stage to 25mm (from the bottom of clamper arm amount to the top of platform), with sliding part during guaranteeing to measure and fabric keeping parallelism and and clothing in contact.The piece of cloth that 11.4cm × 6.4cm cuts is attached to clamping sliding part, the face of the fabric on sliding part is pulled across the face of the fabric in sample panel.Sliding part is placed on fabric, and is attached to load sensor.Movable chuck, until load sensor display is between ~ 1.0 – 2.0gf.Then by its travelling backwards, until load sensor reading is 0.0gf.Now measure, and record dynamic friction coefficient (kCOF).For each process, measure at least four horizontal survey fabrics, and by results averaged.
1water-soluble cationic polymer, the copolymer of such as acrylamide and methacryl amido-hydroxypropyltrimonium chloride (MAPTAC), purchased from Nalco.
2xiameter (subsidiary of DowCorning (Midland, MI)) is derived from the form of an emulsion with trade name MEM-1788.Percentage by weight is listed with active polydimethylsiloxane alcohol %.
3before joining compositions, with BrijO2 and BrijO10, silylanizing Soybean Milk is changed into the fat liquor of 20 % by weight.The percentage by weight of listing in table is active silyl soybean oil.
4with Nalco1115 purchased from Nalco (Naperville, IL).Percentage by weight is reported with active silica %.
5it is 1.470 that the coefficient of kinetic friction of pure water tester is surveyed
*other optional agent/composition comprise foam inhibitor, structural agent such as based on castor oil hydrogenated (preferably castor oil hydrogenated, anion pre-composition) those, dyestuff, solvent, spice, antiseptic, nacreous mica agent aesthetic property reinforcing agent and/or aesthetic property reinforcing agent.
Should understand, dimension disclosed herein and value are not intended to be strictly limited to quoted exact value.On the contrary, except as otherwise noted, each such dimension is intended to represent described value and around this value functionally equivalency range.Such as, the dimension being disclosed as " 40mm " is intended to represent " about 40mm ".
Unless expressly excluded, or restriction, by the every section of document quoted, comprise any cross reference or Patents or patent application herein, be incorporated herein by reference in full.Quoting of any document is not to its prior art as disclosed herein or claimed any invention; its individually or with any combination of other list of references any, or with reference to, propose, suggestion or disclose any accreditation that this type of is invented.In addition, when any implication of same term in any implication of term in the present invention or definition and the file that is incorporated to way of reference or when defining contradiction, the implication or definition of giving this term in the present invention should be obeyed.
Although illustrate and described concrete aspect of the present invention, it is obvious to those skilled in the art that can make various other without departing from the spirit and scope of the present invention changes and modification.Therefore, purport contains all these change and modification of belonging in the scope of the invention in the following claims herein.

Claims (16)

1. consumer products, described consumer products comprise:
A oil that () is silane-modified, described silane-modified oil comprises:
(i) hydrocarbon chain, described hydrocarbon chain is selected from: fat oil, undersaturated oil and their mixture; And
(ii) with the hydrolysable silyl group group of described hydrocarbon chain covalent bonding; And
(b) antiseptic.
2. consumer products according to claim 1, wherein said consumer product compositions is selected from: the automatic tableware washing of aesthetic care products, hand cleaning product, body wash product, shampoo product, conditioner product, cosmetics, hair removing product, laundry product, clothes washing rinsing additive product, laundry detergent products, hard surface cleaning product, hand dishwashing product, automatic tableware cleaning product, unit dosage form or laundry product, nonwoven product, thin page hygiene paper product and absorbent article product.
3. according to consumer products in any one of the preceding claims wherein, wherein said silane-modified oil comprises and is less than about 10% by the weighing scale of described silane-modified oil, preferably be less than about 5%, be preferably less than about 1%, be preferably less than the siliceous remaining reagent of about 0.1%.
4., according to consumer products in any one of the preceding claims wherein, the described oil of wherein said silane-modified oil is triglycerin ester oil, preferred natural oil, preferred soybean oil.
5. according to consumer products in any one of the preceding claims wherein, wherein said silane-modified oil comprises polymer, and described polymer comprises one or more silanols and/or hydrolyzable siloxy residue.
6. consumer products according to claim 5, wherein said polymer is that one or more monomers described are selected from: acrylic acid N, N-dialkyl aminoalkyl ester by being polymerized the obtained synthetic polymer of one or more monomers, methacrylic acid N, N-dialkyl aminoalkyl ester, N, N-dialkylaminoalkyl acrylamide, N, N-dialkyl aminoalkyl Methacrylamide, quaternized acrylic acid N, N dialkyl aminoalkyl ester, quaternized methacrylic acid N, N-dialkyl aminoalkyl ester, quaternary ammonium N, N-dialkylaminoalkyl acrylamide, quaternary ammonium N, N-dialkyl aminoalkyl Methacrylamide, methacryiamidopropyl-pentamethyl-1,3-propylene-2-alcohol-dichloride ammonium, N, N, N, N', N', N ", N "-seven methyl-N "-3-(1-oxo-2-methyl-2-acrylic) aminopropyl-9-oxo-8-azo-decane-Isosorbide-5-Nitrae, 10-tri-chlorination three ammonium, vinylamine and derivant thereof, allylamine and derivant thereof, vinyl imidazole, quatemized vinylimidazol and poly (dially dialkyl) ammonium chloride, Ν, Ν-dialkylacrylamides, Methacrylamide, Ν, Ν-dialkyl methacrylamides, acrylic acid C 1-C 12arrcostab, acrylic acid C 1-C 12hydroxy alkyl ester, acrylic acid poly alkylene glycol ester, methacrylic acid C 1-C 12arrcostab, methacrylic acid C 1-C 12hydroxy alkyl ester, methacrylic acid poly alkylene glycol ester, styrene, butadiene, isoprene, butane, isobutene., vinyl acetate, vinyl alcohol, vinyl formamide, vinyl acetamide, vinyl alkyl ethers, vinylpyridine, vinyl pyrrolidone, vinyl imidazole, caprolactam, acrylic acid, methacrylic acid, maleic acid, vinyl sulfonic acid, styrene sulfonic acid, acrylamido propyl group methanesulfonic acid (AMPS), their salt, and their mixture, preferred isobutene..
7. the consumer products according to any one of claim 5-6, wherein said polymer has and is greater than about 500 or be less than about 8,000, the preferably molecular weight of about 500 to about 8,000.
8., according to consumer products in any one of the preceding claims wherein, wherein said silane-modified oil comprises:
I oil that () average per molecule is silane-modified, is less than the hydrolysable silyl group group of 1.2 covalent bondings;
(ii) oil that average per molecule is silane-modified, is greater than the hydrolysable silyl group group of 5.0 covalent bondings; Or
(iii) oil that average per molecule is silane-modified, the hydrolysable silyl group group of about 0.7 to about 2.4 covalent bonding.
9., according to consumer products in any one of the preceding claims wherein, wherein said silane-modified oil is the form of granule, and described granule comprises:
A () has the particle cores on surface between face; With
B () is attached to the described silane-modified oil on surface between described.
10. according to consumer products in any one of the preceding claims wherein, wherein with oil silane-modified described in one or more surfactant emulsifies.
11. according to consumer products in any one of the preceding claims wherein, and wherein said antiseptic is selected from:
I () antimicrobial, it is preferably selected from: benzalkonium chloride, benzethonium chloride, benzoic acid or its salt, benzylalcohol, boric acid or its salt, hexadecylpyridinium chloride cetyl trimethyl ammonium bromide, methaform, chlorocresol, CHG, chlorhexidine acetate, cresol, ethanol, hydantoin, imidazolidinyl urea, metacresol, methyl parahydroxybenzoate, nitromersol, o-phenyl phenol, p-Hydroxybenzoate, phenol, phenylmercuric acetate/phenylmercuric nitrate, propyl p-hydroxybenzoate, sodium benzoate, sorbic acid or its salt, bata-phenethyl alcohol, thimerosal and their mixture;
(ii) antioxidant, it is preferably selected from a-tocopherol acetas, acetone sulfite., acetylcysteine, ascorbic acid, ascorbyl palmitate, butylated hydroxyanisol (BHA), Yoshinox BHT (BHT), citric acid, cysteine, cysteine hydrochloride, natural d-alpha-tocopherol, synthesis d-alpha-tocopherol, dithiothreitol, DTT, thioglycerol, nordihydroguaiaretic acid, propyl gallate, sodium sulfite, sodium sulfoxylate formaldehyde, sodium pyrosulfite, sodium sulfite, sodium thiosulfate, thiourea, tocopherol, and their mixture, and
(iii) their mixture.
12. according to consumer products in any one of the preceding claims wherein, wherein said consumer products also comprise hydroxy-functional organic substance, described hydroxy-functional organic substance is preferably selected from: monosaccharide, disaccharide, oligosaccharide, polysaccharide, functionalized monosaccharide, functionalized disaccharide, functionalized oligomeric sugar, functionalized polysaccharide, cellulose, guar gum, starch, cyclodextrin, hydroxypropyl guar gum, hydroxypropyl cellulose, guar hydroxypropyltrimonium chloride, Polyquaternium-10, organosiloxane material, polymer, polyvinyl, hydroxy-end capped polybutadiene, glycol, polyglycols, ether, polyethers, polyalkylene oxide, poly(ethylene oxide), poly(propylene oxide), their derivant, and their mixture, preferably have organic siloxane material, preferred dimethiconol.
13. according to consumer products in any one of the preceding claims wherein, and wherein said consumer products also comprise:
(i) hydroxy-functional inorganic particle, it is preferably selected from metal-oxide, and described metal-oxide is selected from silicon dioxide, titanium dioxide, aluminium oxide and their mixture; Metallocene; Zeolite; Clay; Pigment; And their mixture;
(ii) particle benefit agent, it is preferably selected from pigment, clay, personal care actives matter, antiperspirant active, the liquid active substance of encapsulating and their mixture; Preferred perfume microcapsule;
(iii) spice; Or
(iv) their mixture.
14. according to consumer products in any one of the preceding claims wherein, and wherein said consumer products comprise silane-modified oil base gel network, and described silane-modified oil base gel network comprises the product of following material:
(a) described silane-modified oil;
(b) described hydroxy-functional organic substance; And
(c) water;
Wherein:
I at least some in the described hydrolysable silyl group group of () described silane-modified oil with the hydrolysis of described water and condensation, thus forms silicone cross-linked key between covalent molecule between silane-modified oil molecule in described crosslinked silane-modified oil; And
(ii) described crosslinked silane-modified oil and described intermolecular silicone cross-linked key full cross-linked to form networking gel; And
D () carrier, wherein said carrier is aqueous or nonaqueous.
15. 1 kinds, for the treatment of the method on surface, said method comprising the steps of:
A () will be applied to described surface according to consumer products in any one of the preceding claims wherein; And
B water is optionally applied to described surface by ().
16. methods according to claim 15, wherein processed described surface is selected from fabric, yarn fabric, leather, nonwoven substrate, woven base, fiber, carpet, house decorative material, glass, pottery, skin, hair, fingernail, stone material, masonry, timber, plastics, paper wood, cardboard, metal, packaging, package component and their combination.
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